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91.
DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex 下载免费PDF全文
Cheng‐Gen Zhang Shu‐Yuan Yu Liaoyun Zhang Huayi Li Zhi‐Xiang Wang 《Journal of polymer science. Part A, Polymer chemistry》2015,53(4):576-585
DFT computations have been performed to investigate the mechanism of H2‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H2 can react with the deactivated [Zr]?pMS?PPn facilely, which displace functionalized pMS?PPn chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585 相似文献
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针对传统红外图像增强算法中细节模糊及过度增强的问题,提出了一种基于Retinex理论与概率非局部均值相结合的红外图像增强方法.首先通过单尺度Retinex方法调整图像中过暗与过亮部分的灰度级;然后利用概率非局部均值对图像进行分解处理得到基本层与细节层,对基本层采用直方图均衡化拉伸对比度,对细节层采用非线性函数进行增强;最后,将不同层次的结果融合得到对比度与细节增强的红外图像.用该方法对多组不同场景的红外图像进行仿真实验,并将其与多种增强方法进行主、客观对比分析,结果表明所提方法在红外图像的细节及对比度增强方面都获得了更好的效果. 相似文献
95.
The stable phase equilibria of quaternary systems LiBr-NaBr-MgBr2-H2O and LiBr-KBr-MgBr2-H2O at 298.15 K were studied by both experimental measurement(isothermal solution saturation method) and theoretical prediction(Pitzer model). The solubilities of the saturated solution have been determined experimentally and two stable phase diagrams and relevant water diagrams of the two quaternary systems were obtained. Results show that quaternary system LiBr-NaBr-MgBr2-H2O is hydrate II type as NaBr and NaBr·2H2O coexistence. Its phase diagram consists of only one invariant point, four univariant curves, and five crystallization fields. The quaternary system LiBr-KBr-MgBr2-H2O is a complex type as the double salt KBr·MgBr2·6H2O formed. In addition to this double salt, the three single salts LiBr·2H2O, KBr and MgBr2·6H2O also crystallize. In this paper, the solubilities of phase equilibria in above quaternary systems were also calculated by the Pitzer's electrolyte solution model. All the needed parameters can be obtained from the literature or be fitted by experimental data. On the Basis of the experimental and calculated results, the phase diagram of the quaternary system was plotted for comparison. It shows that the calculation results are consistent with the experimental ones. 相似文献
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Experimental Mechanics - There have been relatively few studies on mechanical properties of nanomaterials under high strain rates, mainly due to the lack of capable nanomechanical testing devices.... 相似文献
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Kinetics and Catalysis - A series of Cu-SSZ-13@CeO2 catalysts with surface modification with CeO2 was prepared by the modified self-resemble method based on the one-pot synthesized Cu-SSZ-13... 相似文献
98.
Four kinds of red phosphorescent organic light-emitting devices were fabricated and compared to investigate the effect of interfacial layers for hole transport and electron injection. 1 nm-thick LiF in the device A and C and 1 nm-thick Cs2CO3 in the device B and D were deposited as an electron injection layer between the anode and the electron transport layer, and 5 nm-thick layer of dipyrazion[2,3-f:2′,2′-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile[HATCN] was inserted as a hole transport interfacial layer between the hole injection layer and the hole transport layer only in the device C and D. Under a luminance of 1000 cd/m2, the power efficiencies were 7.6 lm/W and 8.5 lm/W in the device A and B, and 8.6 lm/W and 13.4 lm/W in the device C and D. The quantum efficiency of the device D was 15.8% under 1000 cd/m2 which was somewhat lower than those of the device A and C, but a little higher than that of the device B. The luminance of the device D was much higher than those of the other devices at a given votage. The luminance of the device D at 7 V was 23,710 cd/m2, which was 13.0, 3.4, and 4.0 times higher than those of the device A, B, and C at the same voltage, respectively. 相似文献
99.
Sajeesh Kumar Madhurakkat Perikamana Sang Min Lee Jinkyu Lee Taufiq Ahmad Min Suk Lee Hee Seok Yang Heungsoo Shin 《Macromolecular bioscience》2019,19(4)
Plant derived flavonoids have not been well explored in tissue engineering applications due to difficulties in efficient formulations with biomaterials for controlled presentation. Here, the authors report that surface coating of epigallocatechin gallate (EGCG) on polymeric substrates including poly (L‐lactic acid) (PLLA) nanofibers can be performed via oxidative polymerization of EGCG in the presence of cations, enabling regulation of biological functions of multiple cell types implicated in bone regeneration. EGCG coating on the PLLA nanofiber promotes osteogenic differentiation of adipose‐derived stem cells (ADSCs) and is potent to suppress adipogenesis of ADSCs while significantly reduces osteoclastic maturation of murine macrophages. Moreover, EGCG coating serves as a protective layer for ADSCs against oxidative stress caused by hydrogen peroxide. Finally, the in vivo implantation of EGCG‐coated nanofibers into a mouse calvarial defect model significantly promotes the bone regeneration (61.52 ± 28.10%) as compared to defect (17.48 ± 11.07%). Collectively, the results suggest that EGCG coating is a simple bioinspired surface modification of polymeric biomaterials and importantly can thus serve as a promising interface for tuning activities of multiple cell types associated with bone fracture healing. 相似文献
100.
Prof. Jen-Shyang Ni Tianliang Min Yaxi Li Menglei Zha Dr. Pengfei Zhang Prof. Chun Loong Ho Prof. Kai Li 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(25):10265-10271
Planar luminogens have encountered difficulties in overcoming intrinsic aggregation-caused emission quenching by intermolecular π-π stacking interactions. Although excited-state double-bond reorganization (ESDBR) can guide us on designing planar aggregation-induced emission (AIE) luminogens (AIEgens), its mechanism has yet been elucidated. Major challenges in the field include methods to efficiently restrict ESDBR and enhance AIE performance without using bulky substituents (e.g., tetraphenylethylene and triphenylamine). In this study, we rationally developed fluoro-substituent AIEgens with stronger intermolecular H-bonding interaction for restricted molecular motions and increased crystal density, leading to decreased nonradiative decay rate by one order of magnitude. The adjusted ESDBR properties also show a corresponding response to variation in viscosity. Furthermore, their aggregation-induced reactive oxygen species (ROS) generations have been discovered. The application of such planar AIEgen in treating multidrug-resistant bacteria has been demonstrated in a mouse model. The relationship between ROS generation and distinct E/Z-configurational stacking behaviors have been further understood, providing a design principle for synthesizing planar AIEgen-based photosensitizers. 相似文献