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51.
H. Zhu R. Venkataraman N. Menaa W. Mueller S. Croft A. Berlizov 《Journal of Radioanalytical and Nuclear Chemistry》2008,278(2):359-363
When radionuclides decay by cascading photons, the accuracy of the measured nuclide activity may be affected by true coincidence
summing effects. The effects can be quantified by Monte Carlo simulations that can handle correlated γ-and X-ray emissions
from a radionuclide. Analysis techniques are also available commercially to correct for the effects due to cascading γ-rays.
The MCNP-CP code was used to compute the effects in high purity germanium detectors for several commonly used nuclides and
geometries and the results were compared to measurements and an analysis technique. Excellent agreement in true coincidence
summing corrections predicted by MCNP-CP and the analysis technique was obtained. In addition, the X-ray true coincidence
summing effects were evaluated. 相似文献
52.
53.
Erick Kindt Sandra Bak Mueller Christine Castle Carine M. Boustany‐Kari 《Biomedical chromatography : BMC》2010,24(7):752-758
Biomarkers are an increasingly important constituent of the drug development process, offering the potential of increased efficiency through reduced compound attrition and earlier proof of mechanism and/or efficacy. Assays developed for compound screening that can be directly translated for clinical trials are especially valuable, but their successful adoption requires a careful balance between assay performance and implementation costs. One such ‘fit‐for‐purpose’ biomarker assay, the indirect measurement of pharmacological modulation of sphingolipid biosynthesis and disposition, is presented here. Among spingolipids, numerous ceramide species are readily detectable in different lipoprotein fractions of mammalian plasma, but their parallel quantification can be prohibitively expensive and time consuming. Ceramides differ in their fatty acid moiety, which is readily removed by hydrolysis, yielding a common sphingosine derivative, the measurement of which serves as an indicator of total ceramide. When followed by liquid chromatography tandem mass spectrometry (LC/MS/MS) for detection, robust analyte quantification becomes relatively straightforward. The practical utility of a method developed to be fit for the purpose of rapidly and quantitatively measuring treatment‐induced variations in total ceramide from hamster plasma and individual lipoprotein fractions is described. With a linear calibration range from 0.003 to 33.4 μm sphingosine, precision and accuracy error in plasma‐based quality controls spiked with ceramides was less than 15%. The specificity of the assay for ceramides was also assessed. The simplicity of the method would allow for its potential translation to other preclinical species, as well as for clinical applications in later‐stage drug development. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
54.
Joseph A. Loo Peifeng Hu Patrick McConnell W. Tom Mueller Tomi K. Sawyer Venkataraman Thanabal 《Journal of the American Society for Mass Spectrometry》1997,8(3):234-243
The noncovalent binding of various peptide ligands to pp60src (Src) SH2 (Src homology 2) domain protein (12.9 ku) has been used as a model system for development of electrospray ionization mass spectrometry (ESI-MS) as a tool to study noncovalently bound complexes. SH2 motifs in proteins are critical in the signal transduction pathways of the tyrosine kinase growth factor receptors and recognize phosphotyrosine-containing proteins and peptides. ESI-MS with a magnetic sector instrument and array detection has been used to detect the protein-peptide complex with low-picomole sensitivity. The relative abundances of the multiply charged ions for the complex formed between Src SH2 protein and several nonphosphorylated and phosphorylated peptides have been compared. The mass spectrometry data correlate well to the measured binding constants derived from solution-based methods, indicating that the mass spectrometry-based method can be used to assess the affinity of such interactions. Solution-phase equilibrium constants may be determined by measuring the amount of bound and unbound species as a function of concentration for construction of a Scatchard graph. ESI-MS of a solution containing Src SH2 with a mixture of phosphopeptides showed the expected protein-phosphopeptide complex as the dominant species in the mass spectrum, demonstrating the method’s potential for screening mixtures from peptide libraries. 相似文献
55.
56.
Dr. Christine Beemelmanns Dr. Dominik Nitsch Dr. Christoph Bentz Prof. Dr. Hans-Ulrich Reissig 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(37):8780-8789
A series of γ-indolylketones with fluorine, cyano or alkoxy substituents at the benzene moiety was prepared and subjected to samarium diiodide-promoted cyclization reactions. The desired dearomatizing ketyl cascade reaction forming two new rings proceeded in all cases with high diastereoselectivity, but with differing product distribution. In most cases, the desired annulated tetracyclic compounds were obtained in moderate to good yields, but as second product tetracyclic spirolactones were isolated in up to 29 % yield. The reaction rate was influenced by the substituents at the benzene moiety of the substrate as expected, with electron-accepting groups accelerating and electron-donating groups decelerating the cyclization process. In case of a difluoro-substituted γ-indolylketone a partial defluorination was observed. The intermediate samarium enolate of the tetracyclic products could be trapped by adding reactive alkylating agents as electrophiles delivering products with quarternary carbons. In the case of a dimethoxy-substituted tetracyclic cyclization product a subsequent reductive amination stereoselectively provided a pentacyclic compound that was subsequently N-protected and subjected to a regioselective elimination. The obtained functionalized pentacyclic product should be convertible into the alkaloid brucine by four well-established steps. Overall, the presented report shows that functionalized tetracyclic compounds with different substituents are rapidly available with the samarium diiodide cascade cyclization as crucial step. Hence, analogues of the landmark alkaloid strychnine, for example, with specific fluorine substitutions, should be easily accessible. 相似文献
57.
58.
A. Al-Kahlout S. Heusing T. Mueller N. Aldahoudi M. Quilitz P. W. de Oliveira 《Journal of Sol-Gel Science and Technology》2011,59(3):532-538
Transparent semiconducting ITO:Ti thin films, prepared by a sol–gel process, has been deposited by spin-coating technique
onto alkali-free glass substrates. The as-coated films were annealed in ambient air at 550 °C for 1 h and further annealed
in a reducing atmosphere. The influences of the Ti content in the sol on the surface morphology, microstructure, optical properties
and electrical resistivity have been investigated. These properties were found to depend on the Ti content in the coating
sol. Ti addition led to dense smooth layers with larger crystallite size (20–30 nm). Double layers synthesized with Ti:ITO = 0.53 wt%
and submitted to reducing treatment in forming gas exhibited the lowest sheet resistance R□ = 60 Ω□ with an average transmittance of 87% at 550 nm. 相似文献
59.
Bera MK Hommes P Reissig HU 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(42):11838-11843
Herein, we describe our attempts to systematically prepare a series of oligo(2-thienyl)-substituted pyridine derivatives. The crucial starting material, a β-alkoxy-β-ketoenamide, is easily available on a large scale by the reaction of lithiated methoxyallene with thiophene-2-carbonitrile and thiophene-2-carboxylic acid. This three-component reaction is followed by intramolecular cyclization to yield the suitably functionalized 2,6-di(2-thienyl)-substituted pyridine derivates. The two oxygen atoms allow the programmed activation of positions C-3, C-4, or C-5 of the pyridine ring to perform palladium-catalyzed coupling reactions with thiophene-2-boronic acid or 2-(tributylstannyl)thiophene, and alternatively, reductive removal of groups. With this concept, we were able to prepare five pyridine derivatives with 2-thienyl substituents in the 2,6-, 2,3,6-, 2,4,6-, 2,3,4,6-, and 2,3,5,6-positions. 2,3,4,5,6-Penta(2-thienyl)pyridine was not available with our methods. The UV/Vis and fluorescence spectra of all pyridines were recorded and showed a dependence on the substitution pattern and protonation state. For the protonated 2,3,5,6-tetra(2-thienyl)-substituted pyridine, a Stokes shift of about 180 nm with an emission at 515 nm was observed. 相似文献
60.
Ferse I Langlitz M Kleigrewe K Rzeppa S Lenczyk M Harrer H Cramer B Humpf HU 《Natural product research》2012,26(20):1914-1921
In this study, 10 already described secondary metabolites and 2 unknown metabolites were identified in an extract of Monascus purpureus by high-performance liquid chromatography-diode array detection. The unknown metabolites were isolated and their chemical structures were elucidated. The new metabolites possess the molecular formulas C(21)H(27)NO(4) and C(23)H(31)NO(4). They were named monascopyridines E and F due to their pyridine backbone. The cytotoxicity of the new compounds was studied using immortalised human kidney epithelial cells displaying IC(50) values in the micromolar range. 相似文献