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101.
A theoretical DFT study was employed to confirm the Kolbe-Schmitt reaction mechanism and investigate solvent effects on this reaction. The use of a solvent in the Kolbe-Schmitt reaction is desirable to facilitate a homogeneous reaction mixture and potentially improve the reaction rate. The candidate solvents were designed using computer aided molecular design (CAMD) and tested using DFT solvation calculations. The results from the quantum mechanical calculations were then used to determine the rate constants for each elementary step, the overall reaction yields and the corresponding residence time. The methodology was tested on the reaction without solvent, with solvents reported in the literature, and with the designed solvents. The study revealed that in the presence of solvents with high dielectric constant the reaction becomes reversible, leading to low product yields. 相似文献
102.
PVC profile extrusion compounds have a unique morphology. While other polymers gradually decrease in extrusion die swell with increasing length/thickness (L/D) ratio, PVC profile extrusion compounds have a low die swell, quite independent of the die's L/D ratio in the range of 5 to 20. The fact that the die land length can be changed without changing the extrudate swell is an important consideration, which makes die design and balancing dies simpler and easier for PVC profile extrusion compounds. While other polymers substantially increase extrudate swell with increased shear rate, the swell of the PVC profile compounds is not much affected by shear or extrusion rate. This unique behavior allows wider processing latitude in profile extrusion and faster extrusion rates than with other polymers. Another unique factor in the rheology of PVC profile extrusion compounds is that extrusion die swell increases with increasing melt temperature, while other polymers have decreasing die swell with increasing melt temperature. The unusual rheology of PVC profile extrusion compounds is attributed to its unique melt morphology, where the melt flow units are 1 um bundles and molecules that have low surface to surface interaction and entanglement at low processing temperatures but increased melting and increased entanglement at higher processing temperatures. Other polymers, unlike PVC, have melt flow at the molecular level. 相似文献
103.
The purpose of this work was to examine the possible significance in the formation of metallurgical coke of the anisotropic spherical mesophase exemplified by that found during the carbonization of pitch-like materials, and to ascertain if the various types of optical anisotropy found in coke could form a basis for the characterization of cokes produced from different coals. Vitrains from a wide range of coals were carbonized at temperatures from 370 to 1000 °C and the types and amounts of optical anisotropy in the resulting semi-cokes and cokes were determined from microscopic examination, the anisotropic components being classified according to grain size of the granular mosaics and appearance. The anisotropy developed directly from the isotropic phase, appearing initially as a fine-grained mosaic. With increasing carbonization temperature, this fine-grained mosaic was transformed into progressively coarser-grained anisotropy, the extent of this transformation depending on the rank of the vitrain. It is therefore concluded that the formation, growth and coalescence of anisotropic spherical bodies, such as occurs during the carbonization of pitch, is not a necessary precursor of the mosaic anisotropy in coke. The type and amount of anisotropy developed provide a quantitative means of characterising different cokes. 相似文献
104.
The distribution of plasmalogenase for the hydrolysis of 1-alkenyl-2-acyl-sn-glycero-3-phosphoethanolamine (plasmenylethanolamine) in the subcellular fractions of guinea pig tissues was examined. Plasmalogenase
activity was found in high abundance in the cytosolic fractions of the brain and the heart. Assessment of microsomal marker
enzyme activities in the cytosolic fraction revealed that plasmalogenase activity in the cytosol was not due to microsomal
contaminations. The characteristics of the cytosolic plasmalogenase were very similar to the microsomal enzyme with respect
to the pH profile of the reaction, the presence of divalent cations and Km values for plasmenylethanolamine. However, the cytosolic enzyme was slightly less stable at 55°C than the microsomal enzyme.
Cytosolic enzyme activity was eluted as a broad peak in Sepharose 6B chromatography with an average molecular weight of 250,000.
Our results demonstrate that most of brain plasmalogenase activity is soluble which makes the brain cytosol an excellent source
to initiate the purification of this enzyme. 相似文献
105.
106.
PU YiFei SIARRY Patrick ZHOU JiLiu LIU YiGuang ZHANG Ni HUANG Guo LIU YiZhi 《中国科学:信息科学(英文版)》2014,(7):180-198
In this paper,a set of fractional partial differential equations based on fractional total variation and fractional steepest descent approach are proposed to address the problem of traditional drawbacks of PM and ROF multi-scale denoising for texture image.By extending Green,Gauss,Stokes and Euler-Lagrange formulas to fractional field,we can find that the integer formulas are just their special case of fractional ones.In order to improve the denoising capability,we proposed 4 fractional partial differential equation based multiscale denoising models,and then discussed their stabilities and convergence rate.Theoretic deduction and experimental evaluation demonstrate the stability and astringency of fractional steepest descent approach,and fractional nonlinearly multi-scale denoising capability and best value of parameters are discussed also.The experiments results prove that the ability for preserving high-frequency edge and complex texture information of the proposed denoising models are obviously superior to traditional integral based algorithms,especially for texture detail rich images. 相似文献
107.
Zhang Yingqian Lombardi Michele De Causmaecker Patrick 《Annals of Mathematics and Artificial Intelligence》2021,89(7):615-616
Annals of Mathematics and Artificial Intelligence - 相似文献
108.
Renaud Merlet Louis Winnubst Arian Nijmeijer Mohammad Amirilargani Ernst J. R. Sudhölter Louis C. P. M. de Smet Sara Salvador Cob Pieter Vandezande Matthieu Dorbec Soraya Sluijter Henk van Veen Yvonne VanDelft Ingrid Wienk Petrus Cuperus Subhalaxmi Behera Yusak Hartanto Ivo F. J. Vankelecom Patrick de Wit 《化学,工程师,技术》2021,93(9):1389-1395
Organic solvent nanofiltration (OSN) is gradually expanding from academic research to industrial implementation. The need for membranes with low and sharp molecular weight cutoffs that are able to operate under aggressive OSN conditions is increasing. However, the lack of comparable and uniform performance data frustrates the screening and membrane selection for processes. Here, a collaboration is presented between several academic and industrial partners analyzing the separation performance of 10 different membranes using three model process mixtures. Membrane materials range from classic polymeric and thin film composites (TFCs) to hybrid ceramic types. The model solutions were chosen to mimic cases relevant to today's industrial use: relatively low molar mass solutes (330–550 Da) in n-heptane, toluene, and anisole. 相似文献
109.
Patrick Pimenta R. Cruz Leonardo Cerqueira da Silva Raildo A. Fiuza-Jr Humberto Polli 《应用聚合物科学杂志》2021,138(25):50598
Thermal degradation of PVC occurs in two stages, with each stage subdivided into two substages. The first refers to the dehydrochlorination, where hydrochloric acid is formed, and giving polyene structures. Hitherto, the degradation mechanism and action of hydrochloric acid as a catalyst during the dehydrochlorination stage are poorly known. Recently, the importance of the tacticity has gained attention for its influence on the dehydrochlorination mechanism. The present work focused on the dehydrochlorination stage, studying the molecular structure by FTIR analysis and the kinetic parameters by TGA analysis in Nitrogen atmosphere, based on three mathematical methods: Friedman, Kissinger, and Flynn-Wall-Ozawa. The sample was a pure homopolymer obtained by suspension polymerization. The dehydrochlorination kinetics follows a first order reaction model and occurs by nucleation and growth. The dehydrochlorination begins with the loss of very labile chlorine atoms present in defective and isotactic molecular segments. The formed HCl acts as a catalyst in the degradation. Following 40% conversion, a drop in Ea is observed. After that, chlorine atoms present in syndiotactic and atactic sequences, are released and, added to the large number of polyene chain sequences, and an increase in Ea is observed up to 60% conversion, where the dehydrochlorination stage is concluded. 相似文献
110.
Vladimir Brailovski Patrick Terriault Sergei Prokoshkin 《Journal of Materials Engineering and Performance》2002,11(6):614-621
Shape memory alloys (SMA) suffer from the same impairing mechanisms experienced during cycling loading by classic alloys.
Moreover, SMA fatigue behavior is greatly influenced by thermomechanical cycling through the zone of thermoelastic phase transformation,
which is the basis of shape memory and superelasticity effects. Since the fatigue resistance of any material can be improved
by an appropriate thermomechanical treatment, in the present work combined differential scanning calorimetry and microhardness
testing were used to determine an optimum annealing temperature for the cold-worked Ni-50.1%Ti alloy. The optimization is
based on the assumption that latent heat of transformation is proportional to the mechanical work generated by SMA upon heating,
while material hardness is related to the yield stress of the material. It is supposed that an optimum trade-off in these
two properties guarantees the best dimensional and functional stability of SMA devices. The level and stability of the mechanical
work generated by the material during low-cycle fatigue testing are considered criteria for the material performance and thus
of the validity of the proposed optimization procedure. 相似文献