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21.
Dr. Zhongyun Liu Dr. Yang Liu Dr. Wulin Qiu Prof. William J. Koros 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(35):14987-14993
Glassy polyimide membranes are attractive for industrial applications in sour natural gas purification. Unfortunately, the lack of fundamental understanding of relationships between polyimide chemical structures and their gas transport properties in the presence of H2S constrains the design and engineering of advanced membranes for such challenging applications. Herein, 6FDA-based polyimide membranes with engineered structures were synthesized to tune their CO2/CH4 and H2S/CH4 separation performances and plasticization properties. Under ternary mixed sour gas feeds, controlling polymer chain packing and plasticization tendency of such polyimide membranes via tuning the chemical structures were found to offer better combined H2S and CO2 removal efficiency compared to conventional polymers. Fundamental insights into structure–property relationships of 6FDA-based polyimide membranes observed in this study offer guidance for next generation membranes for sour natural gas separation. 相似文献
22.
Dmytro Strilets Dr. Shixin Fa Arthur Hardiagon Dr. Marc Baaden Prof. Tomoki Ogoshi Dr. Mihail Barboiu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(51):23413-23419
Artificial water channels mimicking natural aquaporins (AQPs) can be used for selective and fast transport of water. Here, we quantify the transport performances of peralkyl-carboxylate-pillar[5]arenes dimers in bilayer membranes. They can transport ≈107 water molecules/channel/second, within one order of magnitude of the transport rates of AQPs, rejecting Na+ and K+ cations. The dimers have a tubular structure, superposing pillar[5]arene pores of 5 Å diameter with twisted carboxy-phenyl pores of 2.8 Å diameter. This biomimetic platform, with variable pore dimensions within the same structure, offers size restriction reminiscent of natural proteins. It allows water molecules to selectively transit and prevents bigger hydrated cations from passing through the 2.8 Å pore. Molecular simulations prove that dimeric or multimeric honeycomb aggregates are stable in the membrane and form water pathways through the bilayer. Over time, a significant shift of the upper vs. lower layer occurs initiating new unexpected water permeation events through toroidal pores. 相似文献
23.
Shuzhen Li Bo Lu Xiaoyu Fang Prof. Dongpeng Yan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(50):22812-22819
Smart molecular crystals with light-driven mechanical responses have received interest owing to their potential uses in molecular machines, artificial muscles, and biomimetics. However, challenges remain in control over both the dynamic photo-mechanical behaviors and static photonic properties of molecular crystals based on the same molecule. Herein, we show the construction of isostructural co-crystals allows their light-induced cracking and jumping behaviors (photosalient effect) to be controlled. Hydrogen-bonded co-crystals from 4-(1-naphthylvinyl)pyridine ( NVP ) with co-formers (tetrafluoro-4-hydroxybenzoic acid ( THA ) and tetrafluorobenzoic acid ( TA )) crystallize as isostructural crystals, but have different static and dynamic photo-mechanical behaviors. These differences are due to alternations in the orientation of NVP and hydrogen-bonding modes of the co-formers. After light activation, the 1D NVP-TA crystal splits and shears off within 1 s. For NVP-THA , its photostability and high quantum yield give novel photonic properties, including low optical waveguide loss, highly polarized anisotropy, and efficient up-conversion fluorescence. 相似文献
24.
Ruirui Xu Kun Wang Haoying Liu Prof. Dr. Weijun Tang Dr. Huaming Sun Prof. Dr. Dong Xue Prof. Dr. Jianliang Xiao Prof. Dr. Chao Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(49):22143-22148
A ruthenium-catalyzed formal anti-Markovnikov hydroamination of allylic alcohols for the synthesis of chiral γ-amino alcohols is presented. Proceeding via an asymmetric hydrogen-borrowing process, the catalysis allows racemic secondary allylic alcohols to react with various amines, affording enantiomerically enriched chiral γ-amino alcohols with broad substrate scope and excellent enantioselectivities (68 examples, up to >99 % ee). 相似文献
25.
In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance. 相似文献
26.
Yong-Jin Zhao Jian-Ping Ma Jianzhong Fan Yan Geng Yu-Bin Dong 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(6):605-615
The tridentate organic ligand 4,4′,4′′‐(4,4,8,8,12,12‐hexamethyl‐8,12‐dihydro‐4H‐benzo[9,1]quinolizino[3,4,5,6,7‐defg]acridine‐2,6,10‐triyl)tribenzoic acid ( H3L ) has been synthesized (as the methanol 1.25‐solvate, C48H39NO6·1.25CH3OH). As a donor–acceptor motif molecule, H3L possess strong intramolecular charge transfer (ICT) fluorescence. Through hydrogen bonds, H3L molecules construct a two‐dimensional (2D) network, which pack together into three‐dimensional (3D) networks with an ABC stacking pattern in the crystalline state. Based on H3L and M(NO3)2 salts (M = Cd and Zn) under solvothermal conditions, two metal–organic frameworks (MOFs), namely, catena‐poly[[triaquacadmium(II)]‐μ‐10‐(4‐carboxyphenyl)‐4,4′‐(4,4,8,8,12,12‐hexamethyl‐8,12‐dihydro‐4H‐benzo[9,1]quinolizino[3,4,5,6,7‐defg]acridine‐2,6‐diyl)dibenzoato], [Cd(C48H37NO6)(H2O)3]n, I , and poly[[μ3‐4,4′,4′′‐(4,4,8,8,12,12‐hexamethyl‐8,12‐dihydro‐4H‐benzo[9,1]quinolizino[3,4,5,6,7‐defg]acridine‐2,6,10‐triyl)tribenzoato](μ3‐hydroxido)zinc(II)], [Zn2(C48H36NO6)(OH)]n, II , were synthesized. Single‐crystal analysis revealed that both MOFs adopt a 3D structure. In I , partly deprotonated HL 2? behaves as a bidentate ligand to link a CdII ion to form a one‐dimensional chain. In the solid state of I , the existence of weak interactions, such as O—H…O hydrogen bonds and π–π interactions, plays an essential role in aligning 2D nets and 3D networks with AB packing patterns for I . The deprotonated ligand L 3? in II is utilized as a tridentate building block to bind ZnII ions to construct 3D networks, where unusual Zn4O14 clusters act as connection nodes. As a donor–acceptor molecule, H3L exhibits fluorescence with a photoluminescence quantum yield (PLQY) of 70% in the solid state. In comparison, the PL of both MOFs is red‐shifted with even higher PLQYs of 79 and 85% for I and II , respectively. 相似文献
27.
A. Othman Almatroud Amina-Aicha Khennaoui Adel Ouannas Giuseppe Grassi M. Mossa Al-sawalha Ahlem Gasri 《Entropy (Basel, Switzerland)》2020,22(12)
This article proposes a new fractional-order discrete-time chaotic system, without equilibria, included two quadratic nonlinearities terms. The dynamics of this system were experimentally investigated via bifurcation diagrams and largest Lyapunov exponent. Besides, some chaotic tests such as the 0–1 test and approximate entropy (ApEn) were included to detect the performance of our numerical results. Furthermore, a valid control method of stabilization is introduced to regulate the proposed system in such a way as to force all its states to adaptively tend toward the equilibrium point at zero. All theoretical findings in this work have been verified numerically using MATLAB software package. 相似文献
28.
The sonochemical activity and the radial dynamics of a harmonically excited spherical bubble are investigated numerically. A detailed model is employed capable to calculate the chemical production inside the bubble placed in water that is saturated with oxygen. Parameter studies are performed with the control parameters of the pressure amplitude, the forcing frequency and the bubble size. Three different definitions of collapse strengths (extracted from the radius vs. time curves) are examined and compared with the chemical output of various species. A mathematical formula is established to estimate the chemical output as a function of the collapse strength; thus, the chemical activity can be predicted without taking into account the chemical kinetics into the bubble model. The calculations are carried out by an in-house code exploiting the high processing power of professional graphics cards (GPUs).The results shown that chemical activity can be approximated qualitatively from the values of relative expansion. This could be helpful in order to optimise chemical output of sonochemical reactors either from measurement data or simulations as well. 相似文献
29.
以三缺位Keggin型硅钨酸盐为前驱体,采用化学沉淀法成功合成出2例新型纳米材料M_3SiW_9(M=Cu.,Co.)。其中,Cu_3SiW_9表现为新颖的纳米晶须形貌,Co_3SiW_9表现为尺寸均一的球形纳米颗粒。经过一系列控制实验证明,通过掺杂不同类型的金属离子可以调控M_3SiW_9的形貌。我们对产生该现象的机理进行了合理推测。此外,使用荧光素钠作为掺杂剂可使Cu_3SiW_9纳米晶须具有优良的光致发光性能,测试表明,多酸并未淬灭荧光素钠的发光,复合材料在510 nm具有明显的发射波长。最后,我们对Cu_3SiW_9纳米晶须负载CdS量子点后的光催化产氢性质进行了研究。结果表明,当Cu_3SiW_9与CdS的质量比为1∶1时,复合材料的产氢效率约为纯CdS量子点的10倍。这也证实多金属氧酸盐的存在可以有效抑制CdS量子点光生电子与空穴的复合,从而大幅提高其光解水产氢的效率。 相似文献
30.
Qi-Jun Li Ya-Jie Ren Qin Xie Min Wu Hua-Xing Feng Li-Mei Zheng Hua-Xin Zhang Jin-Qiao Long Tian-Shun Wang 《应用有机金属化学》2020,34(10):e5813
Two nickel complexes, [Ni(tpen)](ClO4)2.0.5CH3COCH3 ( 1 ) and [Ni(tpbn)](ClO4)2 ( 2 ), of tetrapyridyl ligands N,N,N′,N′-tetrakis(2-pyridyl-methyl)-1,2-ethanediamine (tpen) and N,N,N′,N′-tetrakis(2-pyridyl-methyl)-1,4-butanediamine (tpbn) were prepared and their catalysis for water oxidation reaction (WOR) studied. In 0.1 M phosphate buffer solution (PBS) of pH 8.0, complex 1 is a homogeneous molecular catalyst with an overpotential of ~440 mV and a Faradaic efficiency of 89%. At pH ≥ 9.0, complex 1 degraded gradually during the catalytic process and formed NiOx composite (nickel oxide with general formula NixOyHz) active for WOR. In contrast, complex 2 deteriorated under measured conditions (pH 8.0–12.0) and formed NiOx composite active for WOR. The NiOx composite derived from 1 in 0.1 M PBS at pH 11.0 showed an activity with an overpotential of ~500 mV, a Tafel slope of ~90 mV/decade and a Faradaic efficiency of 97%. Mechanisms were proposed for water oxidation catalyzed by 1 and 2 . This work revealed that the catalytic activity of the nickel complexes was related to the flexibility of the tetrapyridyl ligands and the adaptability of the coordination sphere of the nickel(II) center. 相似文献