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201.
Thomas Wittmann Dr. Renée Siegel Nele Reimer Dr. Wolfgang Milius Prof. Dr. Norbert Stock Prof. Dr. Jürgen Senker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):314-323
The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH2 by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N2 and H2O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m2 g?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with 1H‐27Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking. 相似文献
202.
Galia Pozina Elizaveta I. Girshova Konstantin M. Morozov Konstantin A. Ivanov Anton Yu. Egorov Mikhail A. Kaliteevski 《Annalen der Physik》2019,531(6)
Enhancement of spontaneous emission in a resonant Bragg quantum well (QW) structure with 60 periods of triple InAs monolayers embedded in a GaAs matrix is studied experimentally and theoretically. From measurements of the time‐resolved photoluminescence, besides the QW exciton at 1.47 eV, a specific super‐radiant (SR) emission demonstrating nonlinear properties is found. The SR mode shows a near‐quadratic dependence of intensity on excitation power, while its energy position follows the Bragg condition. It is revealed that the SR mode shows a peculiar non‐monotonic dependence of intensity on direction, with a maximum observed at approximately 40°. The enhancement in the SR emission at a specific direction is correlated well with suggested theoretical consideration of the modal Purcell factor for periodic quantum well structures. 相似文献
203.
Yaping Chen Dr. Kun Rui Prof. Jixin Zhu Prof. Shi Xue Dou Dr. Wenping Sun 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(3):703-713
Developing clean and sustainable energies as alternatives to fossil fuels is in strong demand within modern society. The oxygen evolution reaction (OER) is the efficiency-limiting process in plenty of key renewable energy systems, such as electrochemical water splitting and rechargeable metal–air batteries. In this regard, ongoing efforts have been devoted to seeking high-performance electrocatalysts for enhanced energy conversion efficiency. Apart from traditional precious-metal-based catalysts, nickel-based compounds are the most promising earth-abundant OER catalysts, attracting ever-increasing interest due to high activity and stability. In this review, the recent progress on nickel-based oxide and (oxy)hydroxide composites for water oxidation catalysis in terms of materials design/synthesis and electrochemical performance is summarized. Some underlying mechanisms to profoundly understand the catalytic active sites are also highlighted. In addition, the future research trends and perspectives on the development of Ni-based OER electrocatalysts are discussed. 相似文献
204.
Dr. Man-Bo Li Daniels Posevins Dr. Karl P. J. Gustafson Dr. Cheuk-Wai Tai Dr. Andrey Shchukarev Dr. Youai Qiu Dr. Jan-E. Bäckvall 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(1):210-215
A highly selective and efficient oxidative carbocyclization/borylation of enallenols catalyzed by palladium immobilized on amino-functionalized siliceous mesocellular foam (Pd-AmP-MCF) was developed for diastereoselective cyclobutenol synthesis. The heterogeneous palladium catalyst can be recovered and recycled without any observed loss of activity or selectivity. The high diastereoselectivity of the reaction is proposed to originate from a directing effect of the enallenol hydroxyl group. Optically pure cyclobutenol synthesis was achieved by the heterogeneous strategy by using chiral enallenol obtained from kinetic resolution. 相似文献
205.
Tereshchenko E. D. Cherniakov S. M. Yurik R. Yu. Rietveld M. T. Häggström I. 《Radiophysics and Quantum Electronics》2020,62(10):667-676
Radiophysics and Quantum Electronics - We present the results of comparing the total electron content measurements based on GLONASS satellite signals and the EISCAT UHF incoherent scatter radar... 相似文献
206.
Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes 下载免费PDF全文
María González‐Esguevillas Ana Pascual‐Escudero Dr. Javier Adrio Prof. Dr. Juan C. Carretero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4561-4565
The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine. 相似文献
207.
Beyond Stereoselectivity,Switchable Catalysis: Some of the Last Frontier Challenges in Ring‐Opening Polymerization of Cyclic Esters 下载免费PDF全文
Dr. Sophie M. Guillaume Dr. Evgueni Kirillov Dr. Yann Sarazin Prof. Dr. Jean‐François Carpentier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(22):7988-8003
Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted. 相似文献
208.
Development of an LC‐MS/MS method for determining the pharmacokinetics of clonidine following oral administration of Zhenju antihypertensive compound 下载免费PDF全文
Jing Qin Limin Wang Lihong Wu Jun Chen Teng Shen Yongji Li Limei Han Jianxin Wang 《Biomedical chromatography : BMC》2015,29(7):1068-1075
Zhenju antihypertensive compound (ZJAHC) is a combined Chinese–Western medicine formula including clonidine (CLO), hydrochlorothiazide (HCT), rutin, Chrysanthemum indicum extract and pearl powder. Compared with CLO preparations, ZJAHC shows improved activities and decreased adverse effects. It is believed that the side effects of CLO are caused by its high peak plasma concentration. Hence, study of the influence of ZJAHC on the pharmacokinetic behaviors of clonidine seems essential. In present study, the plasma concentrations of CLO were determined with a liquid chromatography–tandem mass spectrometry (LC‐MS/MS) method. The MS/MS transitions monitored for clonidine and internal standard were 230.2 → 213.1 and 152.2 → 110.2, respectively. The analyte was quantified in a single run within 3 min. The pharmacokinetic study showed that the area under the plasma concentration–time curve of CLO in ZJAHC (60 µg/kg CLO) was similar to that of CLO‐HCT‐high (120 µg/kg CLO) but the peak concentration was much lower than that in CLO‐HCT‐high. ZJAHC could enhance the bioavailability without greatly increasing peak concentration of clonidine. This comprehensive effect of enhancing the bioavailability and avoiding the high peak plasma concentration for CLO might mainly result from the co‐contribution of Western medicine and traditional Chinese medicine (TCM), while the effect of TCM was stronger than that of Western medicine. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
209.
Ping Chen Yanhong Hao Xinxin Wang Prof. Dr. Dan Yuan Prof. Dr. Yingming Yao Prof. Dr. Lutz Ackermann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(30):7292-7297
Highly position selective alkylations of N-alkylindoles at C7-positions have been enabled by cationic zirconium complexes. The strategy provides a straightforward access to install alkyl groups at C7-positions of indoles without a complex directing group. Mechanistic studies provided support for the importance of Brønsted acids in the catalytic manifold. 相似文献
210.
Lan-Lan Zhang Dr. Wen-Ke Miao Dr. Li-Jun Ren Yu-Kun Yan Dr. Yue Lin Prof. Wei Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(58):13396-13401
Organic polymers and inorganic clusters belong to two different disciplines and have completely different properties and structures. When a cluster is attached to the backbone of a polymer as a pendant, the resultant hybrid polymers (polyclusters) exhibit unique behaviours totally different from those of conventional polymers owing to the nanoscale size of the cluster and its particular interactions. Herein, the aggregation of a poly(polyoxometalate)—a polynorbornene backbone with inorganic polyoxometalate cluster pendants—upon addition of a non-solvent to its dilute solution is reported. A three-dimensional network of tangled and snake-like nanothreads was observed. Direct visualisation of individual nanoscale clusters enabled identification of single chains within the nanothreads. These observations suggest that during the process of aggregation, the hybrid polymer forms curved or extended chains as a consequence of an armouring effect in which the collapsed cluster pendants wrap around the backbone. The collapse occurs because they become less soluble in the solvent/non-solvent mixture. The extended chains then become entwined and form nanoropes consisting of multiple chains wound around each other. This study provides a deeper understanding of the nature of polyclusters and should also prove useful for their future development and application. 相似文献