Raman chemical imaging provides chemical and spatial information about pharmaceutical drug product. By using resolution methods on acquired spectra, the objective is to calculate pure spectra and distribution maps of image compounds. With multivariate curve resolution-alternating least squares, constraints are used to improve the performance of the resolution and to decrease the ambiguity linked to the final solution. Non negativity and spatial local rank constraints have been identified as the most powerful constraints to be used. 相似文献
Droplet evaporation characterization, although of great significance, is still challenging. The recently developed phase rainbow refractometry (PRR) is proposed as an approach to measuring the droplet temperature, size as well as evaporation rate simultaneously, and is applied to a single flowing n-heptane droplet produced by a droplet-on-demand generator. The changes of droplet temperature and evaporation rate after a transient spark heating are reflected in the time-resolved PRR image. Results show that droplet evaporation rate increases with temperature, from ?1.28 m2/s at atmospheric 293 K to a range of (?1.5, ?8) m2/s when heated to (294, 315) K, agreeing well with the Maxwell and Stefan–Fuchs model predictions. Uncertainty analysis suggests that the main source is the indeterminate gradient inside droplet, resulting in an underestimation of droplet temperature and evaporation rate. With the demonstration on simultaneous measurements of droplet refractive index as well as droplet transient and local evaporation rate in this work, PRR is a promising tool to investigate single droplet evaporation in real engine conditions. 相似文献
The formation of a well-ordered p(2 × 2) overlayer of atomic nitrogen on the Pt(1 1 1) surface and its reaction with hydrogen were characterized with reflection absorption infrared spectroscopy (RAIRS), temperature programmed desorption (TPD), low energy electron diffraction (LEED), Auger electron spectroscopy (AES), and X-ray photoelectron spectroscopy (XPS). The p(2 × 2)-N overlayer is formed by exposure of ammonia to a surface at 85 K that is covered with 0.44 monolayer (ML) of molecular oxygen and then heating to 400 K. The reaction between ammonia and oxygen produces water, which desorbs below 400 K. The only desorption product observed above 400 K is molecular nitrogen, which has a peak desorption temperature of 453 K. The absence of oxygen after the 400 K anneal is confirmed with AES. Although atomic nitrogen can also be produced on the surface through the reaction of ammonia with an atomic, rather than molecular, oxygen overlayer at a saturation coverage of 0.25 ML, the yield of surface nitrogen is significantly less, as indicated by the N2 TPD peak area. Atomic nitrogen readily reacts with hydrogen to produce the NH species, which is characterized with RAIRS by an intense and narrow (FWHM ∼ 4 cm−1) peak at 3322 cm−1. The areas of the H2 TPD peak associated with NH dissociation and the XPS N 1s peak associated with the NH species indicate that not all of the surface N atoms can be converted to NH by the methods used here. 相似文献
A series of low density polyethylene systems has been studied with respect to structural evolution and short-term dielectric breakdown behaviour. All materials were based upon a single polymer, that is commonly used in high voltage applications, but with different additives. In all three of these systems, multiple melting transitions were observed, as a result of molecular fractionation effects during crystallization. In the virgin polymer, a space-filling banded spherulitic morphology was found to develop at low temperatures (102 °C and below) whereas, at higher temperatures, only a few isolated axialites were observed. Inclusion of the antioxidant resulted in greatly increased nucleation densities, such that, at low temperatures, no evidence of spherulitic organisation remained. At higher temperatures, sheaf-like lamellar aggregates developed, which were much smaller and much more numerous than in the case of the virgin polymer. Further addition of dicumyl peroxide (DCP) resulted in the rapid formation of a crosslinked network at 200 °C. Some crosslinking also occurred at 150 °C, but over a much longer timescale. Where extensive crosslinking occurred prior to crystallization, the resulting gel inhibited structural development, such that only a few small, isolated sheaves were able to form at 102 °C. In view of the principal application area of this material, the breakdown strength of each of the above systems was then measured and the whole data set was analysed statistically. When structural factors were considered alongside the statistics, no clear trends emerged to indicate that either the compositional or morphological variations were reflected in the short-term electrical failure processes. 相似文献
This paper undertakes a systematic treatment of the low regularity local wellposedness and ill-posedness theory in Hs andHs for semilinear wave equations with polynomial nonlinearity in u and (e)u. This ill-posed result concerns the focusing type equations with nonlinearity on u and (e)tu. 相似文献
Temperature gradient interaction chromatography (TGIC) was applied for the separation of a complex miktoarm star copolymer which has one polystyrene (PS) arm and three polystyrene-b-polyisoprene (PS-b-PI) diblock copolymer arms. Such miktoarm star polymers are much more difficult to characterize than branched homopolymers since the byproduct, typically polymers with missing arm(s) or coupled products, have not only different molecular weights but also different compositions. TGIC was able to fully separate the byproducts, and the composition of the molecular species corresponding to the different separated elution peaks was determined by two methods, fractionation/NMR and multiple detection (UV and RI). A reasonable agreement between the results of the two methods was obtained. By using the composition found, the corresponding molecular weights were determined by multi-angle light scattering detection. Based on the composition and the molecular weight we were able to identify the structure of the different molecular species. 相似文献
The vibrational dynamics of protein folding is analyzed in the framework of Tsallis statistics. We employ exact expressions
for classical harmonic oscillators by considering the unnormalized constraints. As q→1, we show that these approximations agree with the result of Gaussian network model. 相似文献
A nucleophilic substitution reaction between 4-tert-butylbenzyl bromide and a series of iodide salts has been performed in oil-in-water microemulsions based on either a fatty alcohol ethoxylate or a sugar surfactant. The reaction kinetics was compared with the kinetics of the same reaction performed in a microhomogeneous reaction medium, d-MeOH. Previous results showing a particularly high reactivity in the microemulsion based on the fatty alcohol ethoxylate was confirmed. It was shown that in both microemulsions the reaction rate was almost independent of the choice of counterion to iodide. This indicates that complexation of the cation with the surfactant headgroup, which, in particular, could have taken place with surfactants containing oligooxyethylene chains (a “crown ether effect”), seems not to be of importance.
127I NMR studies, as well as quadrupole splitting experiments performed by 2H NMR, indicate that there is a certain accumulation of iodide at the oil–water interface of the microemulsions. It is difficult to draw any quantitative conclusions in this respect, however.
The results obtained in this study, combined with results from previous investigations of the same reaction, indicate that the unexpectedly high reactivity obtained in the microemulsion based on a surfactant containing an oligooxyethylene headgroup is most probably due to the nucleophile being poorly solvated when present in the headgroup layer of such a microemulsion. Poorly solvated anions are known to be highly reactive nucleophiles. 相似文献