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131.
We determine the probability distribution of the first passage time for a class of non-Markovian processes. This class contains, amongst others, the well-known continuous time random walk (CTRW), which is able to account for many properties of anomalous diffusion processes. In particular, we obtain the mean first passage time for CTRW processes with truncated power-law transition time distribution. Our treatment is based on the fact that the solutions of the non-Markovian master equation can be obtained via an integral transform from a Markovian Langevin process.  相似文献   
132.
A series of 9-borafluorene derivatives, functionalised with electron-donating groups, have been prepared. Some of these 9-borafluorene compounds exhibit strong yellowish emission in solution and in the solid state with relatively high quantum yields (up to 73.6 % for FMesB-Cz as a neat film). The results suggest that the highly twisted donor groups suppress charge transfer, but the intrinsic photophysical properties of the 9-borafluorene systems remain. The new compounds showed enhanced stability towards the atmosphere, and exhibited excellent thermal stability, revealing their potential for application in materials science. Organic light-emitting diode (OLED) devices were fabricated with two of the highly emissive compounds, and they exhibited strong yellow-greenish electroluminescence, with a maximum luminance intensity of >22 000 cd m−2. These are the first two examples of 9-borafluorene derivatives being used as light-emitting materials in OLED devices, and they have enabled us to achieve a balance between maintaining their intrinsic properties while improving their stability.  相似文献   
133.
Two N-methylpyridinium compounds and analogous N-protonated salts of 2- and 2,7-substituted 4-pyridyl-pyrene compounds were synthesised and their crystal structures, photophysical properties both in solution and in the solid state, electrochemical and spectroelectrochemical properties were studied. Upon methylation or protonation, the emission maxima are significantly bathochromically shifted compared to the neutral compounds, although the absorption maxima remain almost unchanged. As a result, the cationic compounds show very large apparent Stokes shifts of up to 7200 cm−1. The N-methylpyridinium compounds have a single reduction at ca. −1.5 V vs. Fc/Fc+ in MeCN. While the reduction process was reversible for the 2,7-disubstituted compound, it was irreversible for the mono-substituted one. Experimental findings are complemented by DFT and TD-DFT calculations. Furthermore, the N-methylpyridinium compounds show strong interactions with calf thymus (ct)-DNA, presumably by intercalation, which paves the way for further applications of these multi-functional compounds as potential DNA-bioactive agents.  相似文献   
134.
Phosphorus nitride imide, PN(NH), is of great scientific importance because it is isosteric with silica (SiO2). Accordingly, a varied structural diversity could be expected. However, only one polymorph of PN(NH) has been reported thus far. Herein, we report on the synthesis and structural investigation of the first high‐pressure polymorph of phosphorus nitride imide, β‐PN(NH); the compound has been synthesized using the multianvil technique. By adding catalytic amounts of NH4Cl as a mineralizer, it became possible to grow single crystals of β‐PN(NH), which allowed the first complete structural elucidation of a highly condensed phosphorus nitride from single‐crystal X‐ray diffraction data. The structure was confirmed by FTIR and 31P and 1H solid‐state NMR spectroscopy. We are confident that high‐pressure/high‐temperature reactions could lead to new polymorphs of PN(NH) containing five‐fold‐ or even six‐fold‐coordinated phosphorus atoms and thus rivalling or even surpassing the structural variety of SiO2.  相似文献   
135.
Bioconversion of l-phenylalanine to 2-phenylethanol using Saccharomyces cerevisiae is connected with the growth of biomass strongly limited by product inhibition. Therefore, fermentation can proceed only at low conversions of l-phenylalanine with very low yield of the desired product, which allows reaching the maximum concentration of 2-phenylethanol, 4 g L?1, in an ordinary batch, fed-batch, or chemostat bioreactor. To minimize capital and operating costs in the bioproduction of chemical specialties where the product inhibits the bioreaction, using a hybrid system based on the application of membrane extraction integrated in the bioreactor to remove the product is a suitable solution. Integration can be done by an external module for membrane extraction or, as a more efficient solution, by an extraction membrane module immersed directly in the bioreactor. Such a hybrid system can be used to remove 2-phenylethanol from the fermentation media and thus to overcome the product inhibition of the biotransformation process. In this paper, a hybrid system consisting of a stirred tank bioreactor (3.5 L) and an immersed extraction hollow fiber membrane module was studied. In the proposed system, the kinetics of 2-phenylethanol extraction from a water solution with and without biomass in the bioreactor to alkanes at different operational conditions was measured. Extraction kinetics was compared with the predictions obtained by a mathematical model. In the hybrid system, two extractive biotransformation experiments were performed and compared with that without product removal. Experimental data were also mathematically predicted with good accuracy between the simulation and the experiment.  相似文献   
136.
A systematic study of the diffusion mechanism of CO2 in commercial 13X zeolite beads is presented. In order to gain a complete understanding of the diffusion process of CO2, kinetic measurements with a zero length column (ZLC) system and a volumetric apparatus have been carried out. The ZLC experiments were carried out on a single bead of zeolite 13X at 38 °C at a partial pressure of CO2 of 0.1 bar, conditions representative of post-combustion capture. Experiments with different carrier gases clearly show that the diffusion process is controlled by the transport inside the macropores. Volumetric measurements using a Quantachrome Autosorb system were carried out at different concentrations. These experiments are without a carrier gas and the low pressure measurements show clearly Knudsen diffusion control in both the uptake cell and the bead macropores. At increasing CO2 concentrations the transport mechanism shifts from Knudsen diffusion in the macropores to a completely heat limited process. Both sets of experiments are consistent with independent measurements of bead void fraction and tortuosity and confirm that under the range of conditions that are typical of a carbon capture process the system is controlled by macropore diffusion mechanisms.  相似文献   
137.
Using a new divergent approach, conjugated triarylborane dendrimers were synthesized up to the 2nd generation. The synthetic strategy consists of three steps: 1) functionalization, via iridium catalyzed C−H borylation; 2) activation, via fluorination of the generated boronate ester with K[HF2] or [N(nBu4)][HF2]; and 3) expansion, via reaction of the trifluoroborate salts with aryl Grignard reagents. The concept was also shown to be viable for a convergent approach. All but one of the conjugated borane dendrimers exhibit multiple, distinct and reversible reduction potentials, making them potentially interesting materials for applications in molecular accumulators. Based on their photophysical properties, the 1st generation dendrimers exhibit good conjugation over the whole system. However, the conjugation does not increase further upon expansion to the 2nd generation, but the molar extinction coefficients increase linearly with the number of triarylborane subunits, suggesting a potential application as photonic antennas.  相似文献   
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