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81.
Jun Zhang Prof. Dr. Michael Dolg 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(43):13909-13912
By state‐of‐the‐art quantum chemical methods, we show that for bulky functional groups like cyclohexane, [20]fullerene, dodecahedrane, and C60, the attractive dispersion interaction can have a greater impact on stereochemistry than the repulsive steric effect, making the compact isomer the more stable one. In particular, for the double C60 adduct of pentacene 1 , the syn isomer should be the main product instead of the anti one inferred in the original synthesis experiment (Y. Murata et al., J. Org. Chem. 1999 , 64, 3483). With and without dispersion interactions taken into account, the Gibbs energy difference ΔG(syn?anti) is ?6.36 and +1.15 kcal mol?1, respectively. This study reminds us that dispersion interactions as well as electrostatic or hyperconjugation effects, etc. can lead to some unusual stereochemical phenomena. 相似文献
82.
A simple, green, and efficient method for the N-tert-butoxycarbonylation of amines by pyridinium 2,2,2- trifluoroacetate ([Py][OTf]) as an efficient and reusable catalyst is reported. In general, electron donating groups on aryl group give rise to the higher yields than electron withdrawing groups. Clean reaction, short reaction times, high yields, reusability of catalyst, and easy preparation of it are some advantages of this work. 相似文献
83.
Because of containing urea groups, flame resistance and smoke releasing behaviors of isocyanate-based polyimide foam (IBPIF) produced using free foaming technology require further improvement. In this work, silica aerogel layers were incorporated into cells of IBPIF through an in situ growth process of silica sol (SS). Compared with silica aerogel particles directly mixed into the foaming slurry, the silica aerogel layers that firmly attached to the pores and surfaces of cells not only provided exceptional thermal insulation and flame protection, but also kept original cellular structure. With increase in ratio of SS mass to IBPIF volume, silica aerogel incorporation dosage was gradually increased. Accompanied by flame resistance was obviously improved and smoke releasing behavior was effectively suppressed. Those were indicated by the improved limiting oxygen index (LOI), decreased heat release rate (HRR), peak of HRR, and specific optical density of smoke (Ds) in trials with pilot flames. Compared with pure IBPIF, when the ratio reached to 5/15 g/cm3, it resulted in LOI increasing from 22.0% to 33.0%, peak of HRR, total smoke production (TSP), and maximum value of Ds decreasing from 174 to 72 kW/m2, 1.11 to 0.37 m2/m2, 45.90 to 17.45, respectively. 相似文献
84.
Dr. Julien Gasnot Clément Botella Dr. Sébastien Comesse Dr. Sami Lakhdar Dr. Carole Alayrac Prof. Annie-Claude Gaumont Prof. Vincent Dalla Dr. Catherine Taillier 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(29):11867-11871
Advances in the field of phosphorus chemistry are documented, by revealing the synthetic utility of previously underutilized quaternary phosphiranium salts (QPrS) as three-chain-atom electrophilic building blocks. Notably, control of their challenging C-centered electrophilicity is disclosed with an expedient synthesis of tertiary β-anilino phosphines as a proof-of-concept. 相似文献
85.
在京津冀一体化、雄安新区建设和"绿水青山就是金山银山"生态文明思想的三大政策背景下,由首都师范大学化学(师范)专业师生组成的京冀科育团队于2019年暑假走进雄安新区,以化学教育为核心、以环境保护为主题、以提升学科核心素养为导向,开展了兼具化学专业特色和教师教育特色的暑期实践活动。 相似文献
86.
Hong Yang Mengqi Li Chong Li Qianfu Luo Ming‐Qiang Zhu He Tian Wei‐Hong Zhu 《Angewandte Chemie (International ed. in English)》2020,59(22):8560-8570
Unprecedented dual aggregation‐induced emission (AIE) behavior based on a steric‐hindrance photochromic system is presented, with incorporation one or two bulky aryl groups, resulting in different flexibleness. The dual AIE behavior of open and closed isomers can be explained by restriction of intramolecular rotation (RIR), restriction of intramolecular vibration (RIV), and intermolecular stacking. The large bulky benzothiophene causes restricted rotation, enhancing the emission of open form in solution and weak π–π molecular packing, thereby efficiently enhancing the luminescence performance in the solid state. With incorporation of two large bulky benzothiophene groups, BBTE possesses the most outstanding AIE activity, undergoing highly efficient and reversible off‐to‐on fluorescence in film upon alternating UV and visible light irradiation along with excellent fatigue resistance. The off‐to‐on fluorescent photoswitch is successfully established in super resolution imaging. 相似文献
87.
Xingtao Wang Yong Wang Taiyang Zhang Xiaomin Liu Yixin Zhao 《Angewandte Chemie (International ed. in English)》2020,59(4):1469-1473
The reduced dimension perovskite including 2D perovskites are one of the most promising strategies to stabilize lead halide perovskite. A mixed‐cation 2D perovskite based on a steric phenyltrimethylammonium (PTA) cation is presented. The PTA‐MA mixed‐cation 2D perovskite of PTAMAPbI4 can be formed on the surface of MAPbI3 (PTAI‐MAPbI3) by controllable PTAI intercalation by either spin coating or soaking. The PTAMAPbI4 capping layer can not only passivate PTAI‐MAPbI3 perovskite but also act as MA+ locker to inhibit MAI extraction and significantly enhance the stability. The highly stable PTAI‐MAPbI3 based perovskite solar cells exhibit a reproducible photovoltaic performance with a champion PCE of 21.16 %. Such unencapsulated devices retain 93 % of initial efficiency after 500 h continuous illumination. This steric mixed‐cation 2D perovskite as MA+ locker to stabilize the MAPbI3 is a promising strategy to design stable and high‐performance hybrid lead halide perovskites. 相似文献
88.
Ming Zhu Guanyao Wang Xing Liu Bingkun Guo Gang Xu Zhongyi Huang Minghong Wu Hua‐Kun Liu Shi‐Xue Dou Chao Wu 《Angewandte Chemie (International ed. in English)》2020,59(16):6596-6600
Sodium metal is an ideal anode material for metal rechargeable batteries, owing to its high theoretical capacity (1166 mAh g?1), low cost, and earth‐abundance. However, the dendritic growth upon Na plating, stemming from unstable solid electrolyte interphase (SEI) film, is a major and most notable problem. Here, a sodium benzenedithiolate (PhS2Na2)‐rich protection layer is synthesized in situ on sodium by a facile method that effectively prevents dendrite growth in the carbonate electrolyte, leading to stabilized sodium metal electrodeposition for 400 cycles (800 h) of repeated plating/stripping at a current density of 1 mA cm?2. The organic salt, PhS2Na2, is found to be a critical component in the protection layer. This finding opens up a new and promising avenue, based on organic sodium slats, to stabilize sodium metals with a protection layer. 相似文献
89.
Climate changes, emerging species of plant pests, and deficits of clean water and arable land have made availability of food to the ever-increasing global population a challenge. Excessive use of synthetic pesticides to meet ever-increasing production needs has resulted in development of resistance in pest populations, as well as significant ecotoxicity, which has directly and indirectly impacted all life-forms on earth. To meet the goal of providing safe, sufficient, and high-quality food globally with minimal environmental impact, one strategy is to focus on targeted delivery of pesticides using eco-friendly and biodegradable carriers that are derived from naturally available materials. Herein, we discuss some of the recent approaches to use biodegradable matrices in crop protection, while exploring their design and efficiency. We summarize by discussing associated challenges with the existing approaches and future trends that can lead the world to more sustainable agricultural practices. 相似文献
90.