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61.
We use molecular dynamics computer simulations to investigate the relaxation dynamics of a simple model for a colloidal gel at a low volume fraction. We find that due to the presence of the open spanning network this dynamics shows at low temperature a nontrivial dependence on the wave vector which is very different from the one observed in dense glass-forming liquids. At high wave vectors the relaxation is due to the fast cooperative motion of the branches of the gel network, whereas at low wave vectors the overall rearrangements of the heterogeneous structure produce the relaxation process.  相似文献   
62.
We prove surface and volume mean value formulas for classical solutions to uniformly parabolic equations in the divergence form with low regularity of the coefficients. We then use them to prove the parabolic strong maximum principle and the parabolic Harnack inequality. We emphasize that our results only rely on the classical theory, and our arguments follow the lines used in the original theory of harmonic functions. We provide two proofs relying on two different formulations of the divergence theorem, one stated for sets with almost C1-boundary, the other stated for sets with finite perimeter.  相似文献   
63.
We investigate the degradation path of MAPbI3 (MA=methylammonium) films over flat TiO2 substrates at room temperature by means of X‐ray diffraction, spectroscopic ellipsometry, X‐ray photoelectron spectroscopy, and high‐resolution transmission electron microscopy. The degradation dynamics is found to be similar in air and under vacuum conditions, which leads to the conclusion that the occurrence of intrinsic thermodynamic mechanisms is not necessarily linked to humidity. The process has an early stage, which drives the starting tetragonal lattice in the direction of a cubic atomic arrangement. This early stage is followed by a phase change towards PbI2. We describe how this degradation product is structurally coupled with the original MAPbI3 lattice through the orientation of its constituent PbI6 octahedra. Our results suggest a slight octahedral rearrangement after volatilization of HI+CH3NH2 or MAI, with a relatively low energy cost. Our experiments also clarify why reducing the interfaces and internal defects in the perovskite lattice enhances the stability of the material.  相似文献   
64.
The aim of this work was to develop a new method to determine the mercury (Hg) concentrations in phosphate rock using a dedicated analytical instrument (the DMA80 Tricell by Milestone) that employs an integrated sequence of thermal decomposition followed by catalyst conversion, amalgamation and atomic absorption spectrophotometry. However, this instrument underestimates Hg concentrations when phosphorite and apatite rocks are investigated with a classic thermal decomposition treatment that complies with US EPA method 7473.  相似文献   
65.
In this work, the capabilities of solid phase microextraction were exploited in a fully optimized SPME-GC-QqQ-MS analytical approach for hydrazine assay. A rapid and easy method was obtained by a simple derivatization reaction with propyl chloroformate and pyridine carried out directly in water samples, followed by automated SPME analysis in the same vial without further sample handling. The affinity of the different derivatized compounds obtained towards five commercially available SPME coatings was evaluated, in order to achieve the best extraction efficiency. GC analyses were carried out using a GC-QqQ-MS instrument in selected reaction monitoring (SRM) acquisition mode which has allowed the achievement of high specificity by selecting appropriate precursor–product ion couples improving the capability in analyte identification. The multivariate approach of experimental design was crucial in order to optimize derivatization reaction, SPME process and tandem mass spectrometry parameters. Accuracy of the proposed protocol, tested at 60, 200 and 800 ng L−1, provided satisfactory values (114.2%, 83.6% and 98.6%, respectively), whereas precision (RSD%) at the same concentration levels were of 10.9%, 7.9% and 7.7% respectively. Limit of detection and quantification of 4.4 and 8.3 ng L−1 were obtained. The reliable application of the proposed protocol to real drinking water samples confirmed its capability to be used as analytical tool for routine analyses.  相似文献   
66.
An interesting and surprising rearrangement was observed during the reaction of 4-N-benzyl piperazinone derivatives with Lawesson’s reagent as a thionating agent. Investigation into the possible mechanism responsible for these results is reported herein.  相似文献   
67.
A fast analytical method has been developed for the determination of nine amino acids, together with serotonin, in wine samples of different origin and vintage. The method is based on capillary electrophoresis coupled to laser-induced fluorescence detection. Separation was obtained by using a fused-silica capillary (75?μm id, 74.0?cm total length, 60.0?cm length to detector) and a background electrolyte composed of carbonate buffer (20?mM, pH 9.2), applying a 20?kV voltage. Direct hydrodynamic injection of wine samples was made after an original microwave-assisted derivatisation step with 5-(4,6-dichlorotriazinyl)aminofluorescein. Fluorescence was induced by an Ar-Ion laser, exciting at 488?nm. Good linearity (r(2) >0.9990) was obtained for all considered analytes and sensitivity was also good, with limits of detection in the 7-50?ng/mL range. The method was successfully applied for the analysis of commercial Italian wines and thus seems to be suitable for the determination of the relevant amino acids and serotonin, providing good results in terms of accuracy and precision, together with the advantage of a very fast, microwave-assisted derivatisation procedure. Future applications of the method are planned to check for wine adulterations and commercial frauds.  相似文献   
68.
The esterification reaction between carboxylic acids and alcohols has been used as the source of water for the hydrolysis-condensation reactions of difunctional and trifunctional organosilanes. Diphenylsilanediol (DPDO) has been reacted with methacryloxypropyltrimethoxysilane (MPTMS) and glycidoxypropyltrimethoxysilane (GPTMS) and the obtained products have been characterized by vibrational spectroscopy (FT-IR, FT-Raman) nuclear magnetic resonance (NMR) and gel permeation chromatography. The relation between water availability from the in situ water production process (ISWP) and silsesquioxanes morphology has been evaluated in the case of DPDO/MPTMS mixtures, changing molecular features of acids and alcohols. These measurements have shown that the pK of the carboxylic acid used in the esterification reaction has a valuable influence on the silanes cross-linking ability. Acids with low pK values and heteroatoms substituents favor the silane hydrolysis and allow the growth of high molecular weight species. Using acetic acid/ethanol mixture leads to the best results for DPDO/MPTMS reaction, with a narrow distribution of silsesquioxane species. Under the same conditions, the reaction of DPDO with GPTMS produces polymeric species and only avoiding the presence of the difunctional precursor allows to limiting the silsesquioxanes species growth.  相似文献   
69.
The stabilizing action of C(α)-tetrasubstituted α-amino acids inserted into a sequence of short peptides allowed for the first time the preparation of water-soluble nanoparticles of different materials coated with a helix-structured undecapeptide. This peptide coating strongly favors nanoparticle uptake by human immune system cells.  相似文献   
70.
Langmuir-Schaefer (LS) films of copper(II) tetrakis-(isoprpoxy-carbonyl)-phthalocyanine (TiPCuPc) have been deposited onto various solid supports. Its floating film have been characterized at the air-water interface by means of Brewster Angle Microscopy and Langmuir curves. Vibrational modes of multilayer transferred LS film have been studied by Raman spectroscopy and the optical parameters (refractive index n and extinction coefficient k) have been determined in the visible range of the electromagnetic spectrum. Linearly polarized light absorbance measurements have been performed at room temperature in the 400-800 nm spectral range and the average orientation of the phthalocyanine rings have been estimated. Transmission electron microscopy has been also used to characterize the morphological properties of the LS film and a close packed arrangement of the deposited molecules has been observed.  相似文献   
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