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Michelle Galgoci Janel E. Davidson Clinton K. Harrington Dennis L. Hasha Christian T. Goralski 《合成通讯》2013,43(17):2477-2483
A simple method for the preparation of the title compounds via the reaction of dimethyl 2-ethenylcyclopropane-1,1-dicarboxylate with 6M ammonia in methanol is described. 相似文献
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Clifton K. Fagerquist Omar Sultan Michelle Q. Carter 《Journal of the American Society for Mass Spectrometry》2012,23(12):2102-2114
We previously reported the apparent formation of matrix adducts of 3,5-dimethoxy-4-hydroxy-cinnamic acid (sinapinic acid or SA) via covalent attachment to disulfide bond-containing proteins (HdeA, Hde, and YbgS) from bacterial cell lysates ionized by matrix-assisted laser desorption/ionization (MALDI) time-of-flight-time-of-flight tandem mass spectrometry (TOF-TOF-MS/MS) and post-source decay (PSD). We also reported the absence of adduct formation when using ??-cyano-4-hydroxycinnamic acid (CHCA) matrix. Further mass spectrometric analysis of disulfide-intact and disulfide-reduced over-expressed HdeA and HdeB proteins from lysates of gene-inserted E. coli plasmids suggests covalent attachment of SA occurs not at cysteine residues but at lysine residues. In this revised hypothesis, the attachment of SA is preceded by formation of a solid phase ammonium carboxylate salt between SA and accessible lysine residues of the protein during sample preparation under acidic conditions. Laser irradiation at 355?nm of the dried sample spot results in equilibrium retrogradation followed by nucleophilic attack by the amine group of lysine at the carbonyl group of SA and subsequent amide bond formation and loss of water. The absence of CHCA adducts suggests that the electron-withdrawing effect of the ??-cyano group of this matrix may inhibit salt formation and/or amide bond formation. This revised hypothesis is supported by dissociative loss of SA (?224?Da) and the amide-bound SA (?206?Da) from SA-adducted HdeA and HdeB ions by MS/MS (PSD). It is proposed that cleavage of the amide-bound SA from the lysine side-chain occurs via rearrangement involving a pentacyclic transition state followed by hydrogen abstraction/migration and loss of 3-(4-hydroxy-3,5-dimethoxyphenyl)prop-2-ynal (?206?Da). 相似文献
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Chelsea Weir Michelle L. Pantoya Gautham Ramachandran Tim Dallas Daniel Prentice Michael Daniels 《Journal of Electrostatics》2013,71(1):77-83
Composite energetic material response to electrical stimuli was investigated and a correlation between electrical conductivity and ignition sensitivity was examined. The composites consisted of micrometer particle aluminum combined with another metal, metal oxide, or fluoropolymer. Of the nine tested mixtures, aluminum (Al) with copper oxide (CuO) was the only mixture to ignite by electrostatic discharge. Under the loose powder conditions of these experiments, the Al–CuO minimum ignition energy (MIE) is 25 mJ and exhibited an electrical conductivity two orders of magnitude higher than the next composite. This study showed a similar trend in MIE for ignition triggered by a discharged spark compared with a thermal hot wire source. 相似文献
27.
Stark hole-burning spectroscopy is used to investigate the effective dipole moment change of cresylviolet perchlorate (CVP) in various glass and polymer hosts such as ethanol:methanol (EM), polyvinyl alcohol (PVA), poly (2-hydroxyethyl) methacrylate (PHEMA), polyvinylbutyral (PVB), and formamide. The strong correlation between effective dipole moment change of the guest molecule and the holeburning efficiencies of the host matrices illustrates the sensitivity of the dipole moment change as a direct measure of guest-host interactions. Hole-burning is found to be more efficient as the dipole induced reaction field increases. This relationship is discussed in terms of the unusual hole-burning mechanism suggested for this molecule. The effective dipole moment change of cresylviolet perchlorate ranges from 0.14 to 0.59 Debye. 相似文献
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Andrew S. Bell Joseph Bradley Jeremy R. Everett Michelle Knight Jens Loesel John Mathias David McLoughlin James Mills Robert E. Sharp Christine Williams Terence P. Wood 《Molecular diversity》2013,17(2):319-335
The screening files of many large companies, including Pfizer, have grown considerably due to internal chemistry efforts, company mergers and acquisitions, external contracted synthesis, or compound purchase schemes. In order to screen the targets of interest in a cost-effective fashion, we devised an easy-to-assemble, plate-based diversity subset (PBDS) that represents almost the entire computed chemical space of the screening file whilst comprising only a fraction of the plates in the collection. In order to create this file, we developed new design principles for the quality assessment of screening plates: the Rule of 40 (Ro40) and a plate selection process that insured excellent coverage of both library chemistry and legacy chemistry space. This paper describes the rationale, design, construction, and performance of the PBDS, that has evolved into the standard paradigm for singleton (one compound per well) high-throughput screening in Pfizer since its introduction in 2006. 相似文献
29.
Michelle Co Camilla Zettersten Leif Nyholm Per J.R. Sjöberg Charlotta Turner 《Analytica chimica acta》2012
Experiments with birch bark samples have been carried to enable a distinction between extraction and degradation effects during pressurised hot water extraction. Two samples, E80 and E180, contained birch bark extracts obtained after extraction at 80 and 180 °C for up to 45 min, respectively. Two other samples, P80 and P180, were only extracted for 5 min at the two temperatures and were thereafter filtered and hydrothermally treated at 80 and 180 °C, respectively. During the latter treatment, samples were collected at different times to assess the stability of the extracted compounds. An offline DPPH (2,2-diphenyl-1-picrylhydrazyl) assay, as well as a high performance liquid chromatographic separation coupled to an electrochemical detector, were used to determine the antioxidant capacity of the processed samples. The results obtained with the different techniques were compared to assess the yield of the extraction and degradation processes. In addition, an online hyphenated system comprising high performance liquid chromatography coupled to diode-array; electrochemical; and tandem mass spectrometric detection (HPLC-DAD-ECD-MS/MS) was used to study the compositions of the extracts in more detail. The results for the samples processed at 80 °C showed that the extraction reached a steady-state already after 5 min, and that the extracted compounds were stable throughout the entire extraction process. Processing at 180 °C, on the other hand, gave rise to partly degraded extracts with a multitude of peaks in both the diode array and electrochemical detectors, and a higher antioxidant capacity compared to for the extracts obtained at 80 °C. It is concluded that HPLC-DAD-ECD is a more appropriate technique for the determination of antioxidants than the DPPH assay. The mass spectrometric results indicate that one of the extracted antioxidants, catechin, was isomerised to its diastereoisomers; (+)-catechin, (−)-catechin, (+)-epicatechin, and (−)-epicatechin. 相似文献
30.
Michelle Hampson Naomi Driesen Jennifer K. Roth John C. Gore R. Todd Constable 《Magnetic resonance imaging》2010
Functional brain imaging studies have identified a set of brain areas typically activated during cognitive tasks (task-positive brain areas) and another set of brain areas typically deactivated during cognitive tasks (task-negative brain areas). Negative correlations, or anticorrelations, between task-positive and task-negative brain areas have been reported at rest. Furthermore, the strength of these anticorrelations appears to be related to cognitive function. However, studies examining anticorrelations have typically employed global regression or similar analysis steps that force anticorrelated relationships to exist between brain areas. Therefore the validity of these findings has been questioned. Here we examine anticorrelations between a task-negative region in the medial frontal gyrus/anterior cingulate cortex and dorsolateral prefrontal cortex, a classic task-positive area, using an analysis that does not include global regression. Instead, we control for whole-brain correlations in the group-level analysis. Using this approach, we demonstrate that the strength of the functional connection between the medial frontal cortex and the dorsolateral prefrontal cortex is related to cognitive function and that this relationship is not an artifact of global regression. 相似文献