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991.
Foley DA Doecke CW Buser JY Merritt JM Murphy L Kissane M Collins SG Maguire AR Kaerner A 《The Journal of organic chemistry》2011,76(23):9630-9640
On-flow ReactIR and (1)H NMR reaction monitoring, coupled with in situ intermediate characterization, was used to aid in the mechanistic elucidation of the N-chlorosuccinimide mediated transformation of an α-thioamide. Multiple intermediates in this reaction cascade are identified and characterized, and in particular, spectroscopic evidence for the intermediacy of the chlorosulfonium ion in the chlorination of α-thioamides is provided. Further to this, solvent effects on the outcome of the transformation are discussed. This work also demonstrates the utility of using a combination of ReactIR and flow NMR reaction monitoring (ReactNMR) for characterizing complex multicomponent reaction mixtures. 相似文献
992.
X-ray photoelectron spectroscopy (XPS) has been used to investigate the changes in surface composition of three steels as they have undergone heating. The steels were mild steel, and two austenitic stainless steels, commonly designated 304 and 316 stainless steels. XPS measurements were made on the untreated samples, and then following heating for 30 min in vacuo and in a 1 × 10−6 Torr partial pressure of air, at temperatures between 100 °C and 600 °C.Mild steel behaves differently to the two stainless steels under the heating conditions. In mild steel the iron content of the surface increased, with oxygen and carbon decreasing, as a function of increasing temperature. The chemical state of the iron also changed from oxide at low temperatures, to metallic at temperatures above 450 °C.In both stainless steels the amount of iron present in the surface decreased with increasing temperature. The decrease in iron at the surface was accompanied by an increase in the amount of chromium at the steel surface. At temperatures above 450 °C the iron in both 304 and 316 stainless steels showed significant contributions from metallic iron, whilst the chromium present was in an oxide state. In 316 stainless steel heated to 600 °C there was some metallic chromium present in the surface layer.The surfaces heated in air showed the least variation in composition, with the major change being the loss of carbon from the surfaces following heating above 300 °C. There was also a minor increase in the concentration of chromium present on both the stainless steels heated under these conditions. There was also little change in the oxidation state of the iron and chromium present on the surface of these steels. There was some evidence of the thickening of the surface oxides as seen by the loss of the lower binding energy signal in the iron or chromium core level scans.The surfaces heated in vacuum showed a similar trend in the concentration of carbon on the surfaces, however the overall concentration of oxygen decreased throughout the heating of these steels. There were also significant changes in the oxidation state of the iron and chromium on these surfaces with significant amounts or iron and chromium present in the metallic form following heating up to 600 °C.It appears that the carbon contamination on the surfaces plays an important role in the fate of the surface oxide layer for all of the steels heated in a vacuum environment. 相似文献
993.
Linda ShanahanSurajit Sen 《Physica A》2011,390(10):1800-1810
We introduce a stochastic model to study the problem of time evolution and outcome of simple two-party competitions or battles on a lattice where each party randomly deploys its constituents or elements to the lattice. The elements have assigned strength levels that determine how competitive or effective they are against the opponent. In our models, the elements neutralize one another when they are at the same site with a combination of strength levels and numbers determining which one gains control of the site. The competitions last until complete dominance has been established by one side by eliminating the opponents or a draw is achieved (unless the time evolution is terminated via some ad hoc condition). A Markov chain approach is used to describe the time-dependent dynamics of such competitions. The advantage of the approach is that it allows us to develop a theoretical framework for describing competitive systems where a combination of random and correlated events decide the outcome. We use the approach here for studies of highly contentious stochastic battles and for that of a battle with correlated events along with stochastic events. We present the method, a simple illustrative example on how the method works and close by considering two non-trivial cases including one with a combination of stochasticity and correlations. 相似文献
994.
995.
ABSTRACT Energy losses in solar cells caused by the spectral mismatch can be reduced by adapting the solar spectrum using a downconversion material where one higher energy visible photon is ‘cut' into two lower energy near-infrared photons that both can be absorbed by the solar cell. Downconversion with the (Pr3+, Yb3+) couple in YF3 is investigated. Based on analysis of luminescence and diffuse reflectance spectra it is evident that two-step energy transfer takes place from the 3P0 level of Pr3+ (around 490 nm) exciting two Yb3+ to the 2F5/2 level giving emission around 980 nm. The transfer efficiency increases with Yb3+ concentration and is 86% for YF3 doped with 0.5% Pr3+ and 30% Yb3+. Due to concentration quenching the intensity of emission from Yb3+ is strongly reduced and the 2F5/2 emission intensity reaches a maximum for the sample with 0.5% Pr3+ and 2–5% Yb3+ at 300 K. Temperature dependent measurements reveal the role of the Pr3+ 1G4 level in the energy transfer between Pr3+ and Yb3+. Back-transfer of excitation energy from the Yb3+ 2F5/2 level to the 1G4 level of Pr3+ occurs and quenches the Yb3+ emission. The quenching is shown to become more efficient between 4 and 50 K due to faster phonon-assisted energy transfer between the Yb3+ donors. Upon raising the temperature from 50 to 300 K, the luminescence life time of the Yb3+ emission increases again because the small energy difference between the Pr3+ (1G4) level and the Yb3+ (2F5/2) level (~300 cm?1) which makes the 1G4 less efficient as a trap for the excitation energy. The present results give insight into factors involved in the concentration quenching in downconversion materials based on the (Pr3+, Yb3+) couple. 相似文献
996.
Linda Knutsson Freddy Ståhlberg Ronnie Wirestam Matthias J. van Osch 《Magnetic resonance imaging》2013
Purpose
To evaluate whether a non-linear blood ΔR2*-versus-concentration relationship improves quantitative cerebral blood flow (CBF) estimates obtained by dynamic susceptibility contrast (DSC) MRI in a comparison with Xe-133 SPECT CBF in healthy volunteers.Material and Methods
Linear as well as non-linear relationships between ΔR2* and contrast agent concentration in blood were applied to the arterial input function (AIF) and the venous output function (VOF) from DSC-MRI. To reduce partial volume effects in the AIF, the arterial time integral was rescaled using a corrected VOF scheme.Results
Under the assumption of proportionality between the two modalities, the relationship CBF(MRI) = 0.58CBF(SPECT) (r = 0.64) was observed using the linear relationship and CBF(MRI) = 0.51CBF(SPECT) (r = 0.71) using the non-linear relationship.Discussion
A smaller ratio of the VOF time integral to the AIF time integral and a somewhat better correlation between global DSC-MRI and Xe-133 SPECT CBF estimates were observed using the non-linear relationship. The results did not, however, confirm the superiority of one model over the other, potentially because realistic AIF signal data may well originate from a combination of blood and surrounding tissue. 相似文献997.
Yugang Yu Zhaofu Hong Linda L. Zhang Liang Liang Chengbin Chu 《European Journal of Operational Research》2013
A Vendor Managed Inventory (VMI) system consists of a manufacturing vendor and a number of retailers. In such a system, it is essential for the vendor to optimally determine retailer selection and other related decisions, such as the product’s replenishment cycle time and the wholesale price, in order to maximize his profit. Meanwhile, each retailer’s decisions on her willingness to enter the system and retail price are simultaneously considered in the retailer selection process. However, the above interactive decision making is complex and the available studies on interactive retailer selection are scarce. In this study, we formulate the retailer selection problem as a Stackelberg game model to help the manufacturer, as a vendor, optimally select his retailers to form a VMI system. This model is non-linear, mixed-integer, game-theoretic, and analytically intractable. Therefore, we further develop a hybrid algorithm for effectively and efficiently solving the developed model. The hybrid algorithm combines dynamic programming (DP), genetic algorithm (GA) and analytical methods. As demonstrated by our numerical studies, the optimal retailer selection can increase the manufacturer’s profit by up to 90% and the selected retailers’ profits significantly compared to non-selection strategy. The proposed hybrid algorithm can solve the model within a minute for a problem with 100 candidate retailers, whereas a pure GA has to take more than 1 h to solve a small sized problem of 20 candidate retailers achieving an objective value no worse than that obtained by the hybrid algorithm. 相似文献
998.
Two popular methods for assigning numerical values to a set of to-be-judged objects in order to capture their relative standing are Direct Rating (DR) and Point Allocation (PA). People using PA distribute a fixed sum of 100 points among the objects, while people using DR rate each object on a fixed scale, typically 0–10, later rescaled to sum to 100. Prior research shows that these methods exhibit distinct profiles when values are ranked from largest to smallest, with DR being more test–retest reliable. But which method best translates people’s inner judgments into outer numerical values (is more valid)? Instead of examining subjective or abstract stimuli, we use objectively verifiable perceptual tasks, namely judgments of line length presented using bar charts. We show that (i) DR is more inter-rater reliable than PA; (ii) DR is more accurate than PA at the individual level; (iii) but there is no difference in accuracy when individual judgments are combined to form group-level estimates; and (iv) DR judgments were improved by using prior knowledge of method bias, whereas PA judgments were not. 相似文献
999.
Edward J. Allen Linda J. S. Allen Armando Arciniega Priscilla E. Greenwood 《随机分析与应用》2013,31(2):274-297
Abstract It is shown how different but equivalent Itô stochastic differential equation models of random dynamical systems can be constructed. Advantages and disadvantages of the different models are described. Stochastic differential equation models are derived for problems in chemistry, textile engineering, and epidemiology. Computational comparisons are made between the different stochastic models. 相似文献
1000.
The purpose of the present study was to examine the effect of prolonged loud reading, intended to induce fatigue, on vocal function in adults with unilateral vocal fold paralysis (UVFP). Subjects were 20 adults, 37–60 years old, with UVFP secondary to recurrent laryngeal nerve paralysis. Subjective ratings and instrumental measures of vocal function were obtained before and after reading. Statistical analysis revealed subjects rated their vocal quality and physical effort for voicing more severely following prolonged loud reading, whereas expert raters did not detect a significant perceptual difference in vocal quality. Reading fundamental frequency (Fo) was significantly increased following prolonged loud reading, as were mean airflow rates at all pitch conditions. Maximum phonation times for comfort and low pitches significantly decreased during posttests. Multiple regression analyses revealed significant associations between ratings of posttest physical effort and select posttest measures. Interpretation of results indicates the prolonged loud reading task was successful in vocally fatiguing most of the UVFP subjects. Key physiologic correlates of vocal fatigue, in individuals with UVFP, include further reduction of glottic efficiency, resulting in decreased regulation of glottic airflow and a temporary destabilization of speaking fundamental frequency. 相似文献