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61.
Short and concise total asymmetric syntheses of (−)-isoretronecanol and (−)-trachelantamidine are reported. Oxidative cleavage of tert-butyl (S,S,S,Z)-7-[N-benzyl-N-(α-methylbenzyl)amino]cyclohept-3-ene-1-carboxylate, followed by hydrogenolysis promoted in situ cyclisation/reduction, which provided rapid access to the bicyclic core within (−)-isoretronecanol. Analogous treatment of the C(1)-epimer gave (−)-trachelantamidine. Overall, the syntheses of (−)-isoretronecanol and (−)-trachelantamidine were completed in eight and seven steps and 20 and 9.5% yield, respectively, from commercially available starting materials. 相似文献
62.
In this work we evaluate the influence of thermal desorber temperature on the analytical response of a swipe-based thermal desorption ion mobility spectrometer (IMS) for detection of trace explosives. IMS response for several common high explosives ranging from 0.1 ng to 100 ng was measured over a thermal desorber temperature range from 60 °C to 280 °C. Most of the explosives examined demonstrated a well-defined maximum IMS signal response at a temperature slightly below the melting point. Optimal temperatures, giving the highest IMS peak intensity, were 80 °C for trinitrotoluene (TNT), 100 °C for pentaerythritol tetranitrate (PETN), 160 °C for cyclotrimethylenetrinitramine (RDX) and 200 °C for cyclotetramethylenetetranitramine (HMX). By modifying the desorber temperature, we were able to increase cumulative IMS signal by a factor of 5 for TNT and HMX, and by a factor of 10 for RDX and PETN. Similar signal enhancements were observed for the same compounds formulated as plastic-bonded explosives (Composition 4 (C-4), Detasheet, and Semtex). In addition, mixtures of the explosives exhibited similar enhancements in analyte peak intensities. The increases in sensitivity were obtained at the expense of increased analysis times of up to 20 seconds. A slow sample heating rate as well as slower vapor-phase analyte introduction rate caused by low-temperature desorption enhanced the analytical sensitivity of individual explosives, plastic-bonded explosives, and explosives mixtures by IMS. Several possible mechanisms that can affect IMS signal response were investigated such as thermal degradation of the analytes, ionization efficiency, competitive ionization from background, and aerosol emission. 相似文献
63.
64.
The complex derived from Taniaphos ligand 4 and CuBr*Me2S catalyzes the asymmetric addition of Grignard reagents to 3-bromopropenyl esters 1 to provide allylic esters 2 in high yields and high chemio-, regio-, and enantioselectivities. The work demonstrates that allylic asymmetric alkylation (AAA) can be done on substrates bearing a heteroatom at the gamma-position. The method is a practical route to chiral, nonracemic allylic alcohols. The use of functionalized substrates 1 or Grignard reagents leads to more complex products 2, which can be further manipulated as demonstrated in conversion to (S)-5-ethyl-2(5H)-furanone 6 and (S)-benzoic acid-cyclopent-2-enyl ester 7. 相似文献
65.
Lagrangian and Eulerian modelling approaches are compared for simulating turbulent dispersion and coalescence of droplets within a spray. Both models predict similar droplet dispersion rates and shifts in droplet size distribution due to coalescence within the spray, over a wide range of droplet and gas flows, and for sprays with different droplet-size distributions at the nozzle exit. The computer time required for simulating coalescence within a steady axisymmetric spray is of a similar order of magnitude regardless of which formulation, Eulerian or Lagrangian, is adopted. However, the Lagrangian formulation is more practical in terms of the range of applicability and ease of implementation. 相似文献
66.
67.
The turbulent dispersion of non-evaporating droplets in an axisymmetric round jet issuing from a nozzle is investigated both experimentally and theoretically. The experimental data set has a well-defined inlet boundary with low turbulence intensity at the nozzle exit, so that droplet dispersion is not affected by the transport of nozzle-generated fluctuating motion into the jet, and is influenced solely by turbulence in the gas phase produced in the shear layer of the jet. This data set is thus ideal for testing algebraic models of droplet fluctuating motion that assume local equilibrium with the turbulence in the gas phase. Moreover, the droplet flux measurements are sufficiently accurate that conservation of the total volume flow of the droplet phase has been demonstrated. A two-fluid turbulence modelling approach is adopted, which uses the k–ε turbulence model and a simple algebraic model that assumes local equilibrium to predict the fluid and droplet turbulent correlations, respectively. We have shown that the k–ε turbulence model lacks generality for predicting the spread of momentum in jets with and without a potential core. However, in general, the model predicts the radial dispersion of droplets in the considered turbulent jet with reasonable accuracy over a broad range of droplet sizes, once deficiencies in the k–ε turbulence model are taken into account. 相似文献
68.
In situ ion beam sputter deposition and X‐ray photoelectron spectroscopy (XPS) of multiple thin layers under computer control for combinatorial materials synthesis 下载免费PDF全文
Thomas A. Wilson Anders J. Barlow Michael L. Foster Mariela Bravo Sanchez Jose F. Portoles Naoko Sano Peter J. Cumpson Ian W. Fletcher 《Surface and interface analysis : SIA》2017,49(1):18-24
Deposition of ultra‐thin layers under computer control is a frequent requirement in studies of novel sensors, materials screening, heterogeneous catalysis, the probing of band offsets near semiconductor junctions and many other applications. Often large‐area samples are produced by magnetron sputtering from multiple targets or by atomic layer deposition (ALD). Samples can then be transferred to an analytical chamber for checking by X‐ray photoelectron spectroscopy (XPS) or other surface‐sensitive spectroscopies. The ‘wafer‐scale’ nature of these tools is often greater than is required in combinatorial studies, where a few square centimetres or even millimetres of sample is sufficient for each composition to be tested. The large size leads to increased capital cost, problems of registration as samples are transferred between deposition and analysis, and often makes the use of precious metals as sputter targets prohibitively expensive. Instead we have modified a commercial sample block designed to perform angle‐resolved XPS in a commercial XPS instrument. This now allows ion‐beam sputter deposition from up to six different targets under complete computer control. Ion beam deposition is an attractive technology for depositing ultra‐thin layers of great purity under ultra‐high vacuum conditions, but is generally a very expensive technology. Our new sample block allows ion beam sputtering using the ion gun normally used for sputter depth‐profiling of samples, greatly reducing the cost and allowing deposition to be done (and checked by XPS) in situ in a single instrument. Precious metals are deposited cheaply and efficiently by ion‐beam sputtering from thin metal foils. Samples can then be removed, studied and exposed to reactants or surface treatments before being returned to the XPS to examine and quantify the effects. Copyright © 2016 The Authors Surface and Interface Analysis Published by John Wiley & Sons Ltd. 相似文献
69.
Adam M. Hawkridge Rebecca B. Wysocky James N. Petitte Kenneth E. Anderson Paul E. Mozdziak Oscar J. Fletcher Jonathan M. Horowitz David C. Muddiman 《Analytical and bioanalytical chemistry》2010,398(2):737-749
The domestic chicken (Gallus domesticus) has emerged as a powerful experimental model for studying the onset and progression of spontaneous epithelial ovarian cancer
(EOC) with a disease prevalence that can exceed 35% between 2 and 7 years of age. An experimental strategy for biomarker discovery
is reported herein that combines the chicken model of EOC, longitudinal plasma sample collection with matched tissues, advanced
mass spectrometry-based proteomics, and concepts derived from the index of individuality (Harris, Clin Chem 20: 1535–1542,
1974). Blood was drawn from 148 age-matched chickens starting at 2.5 years of age every 3 months for 1 year. At the conclusion
of the 1 year sample collection period, the 73 birds that remained alive were euthanized, necropsied, and tissues were collected.
Pathological assessment of resected tissues from these 73 birds confirmed that five birds (6.8%) developed EOC. A proteomics
workflow including in-gel digestion, nanoLC coupled to high-performance mass spectrometry, and label-free (spectral counting)
quantification was used to measure the biological intra-individual variability (CVW) of the chicken plasma proteome. Longitudinal plasma sample sets from two birds within the 73-bird biorepository were selected
for this study; one bird was considered “healthy” and the second bird developed late-stage EOC. A total of 116 proteins from
un-depleted plasma were identified with 80 proteins shared among all sample sets. Analytical variability (CVA) of the label-free proteomics workflow was measured using a single plasma sample analyzed five times and was found to be
≥CVW in both birds for 16 proteins (20%) and in either bird for 25 proteins (31%). Ovomacroglobulin (ovostatin) was found to increase
(p < 0.001) over a 6 month period in the late-stage EOC bird providing an initial candidate protein for further investigation. 相似文献
70.