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Dr. Alexey S. Kiryutin Dr. Grit Sauer Dr. Daniel Tietze Martin Brodrecht Stephan Knecht Prof. Dr. Alexandra V. Yurkovskaya Prof. Dr. Konstantin L. Ivanov Dr. Olga Avrutina Prof. Dr. Harald Kolmar Prof. Dr. Gerd Buntkowsky 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(16):4025-4030
Two-dimensional NMR spectroscopy is one of the most important spectroscopic tools for the investigation of biological macromolecules. However, due to the low sensitivity of NMR spectroscopy, it takes usually from several minutes to many hours to record such spectra. Here, the possibility of detecting a bioactive derivative of the sunflower trypsin inhibitor-1 (SFTI-1), a tetradecapeptide, by combining parahydrogen-induced polarization (PHIP) and ultrafast 2D NMR spectroscopy is shown. The PHIP activity of the inhibitor was achieved by labeling with O-propargyl-l -tyrosine. In 1D PHIP experiments a signal enhancement of a factor of approximately 1200 compared to standard NMR was found. This enhancement permits measurement of 2D NMR correlation spectra of low-concentrated SFTI-1 in less than 10 seconds, employing ultrafast single-scan 2D NMR detection. As experimental examples PHIP-assisted ultrafast single-scan TOCSY spectra of SFTI-1 are shown. 相似文献
65.
O. Guselnikova J.P. Fraser N. Soldatova E. Sviridova A. Ivanov R. Rodriguez A.Y. Ganin P. Postnikov 《Materials Today Chemistry》2022
Covalent functionalization of 2D materials provides a tailored approach towards tuning of their chemical, optical, and electronic properties making the search for new ways to graft small molecules important. Herein, the reaction with (3,5-bis(trifluoromethyl)phenyl)iodonium salt is revealed as an effective strategy for functionalization of MoTe2 thin films. Upon decomposition of the salt, the generated radicals graft covalently as aryl-(CF3)2 groups at the surface of both metallic (1T’) and semiconducting (2H) polymorphs of MoTe2. Remarkably, the reactivity of the salt is governed by the electronic structure of the given polymorph. While the functionalization of the metallic MoTe2 occurs spontaneously, the semiconducting MoTe2 requires activation by light. The reaction proceeds with the elimination of oxide from the original films yielding the functionalized products that remain protected in ambient conditions, presenting a viable solution to the ageing of MoTe2 in air. 相似文献
66.
Prof. Isao Fujii Dr. Makoto Hashimoto Kaori Konishi Akiko Unezawa Haruka Sakuraba Kenta Suzuki Harue Tsushima Miho Iwasaki Satsuki Yoshida Akane Kudo Rina Fujita Aika Hichiwa Koharu Saito Dr. Takashi Asano Dr. Jun Ishikawa Dr. Daigo Wakana Dr. Yukihiro Goda Ayumi Watanabe Mamoru Watanabe Yui Masumoto Dr. Junichiro Kanazawa Dr. Hajime Sato Prof. Masanobu Uchiyama 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(22):8542-8548
Shimalactones A and B are neuritogenic polyketides possessing characteristic oxabicyclo[2.2.1]heptane and bicyclo[4.2.0]octadiene ring systems that are produced by the marine fungus Emericella variecolor GF10. We identified a candidate biosynthetic gene cluster and conducted heterologous expression analysis. Expression of ShmA polyketide synthase in Aspergillus oryzae resulted in the production of preshimalactone. Aspergillus oryzae and Saccharomyces cerevisiae transformants expressing ShmA and ShmB produced shimalactones A and B, thus suggesting that the double bicyclo-ring formation reactions proceed non-enzymatically from preshimalactone epoxide. DFT calculations strongly support the idea that oxabicyclo-ring formation and 8π-6π electrocyclization proceed spontaneously after opening of the preshimalactone epoxide ring through protonation. We confirmed the formation of preshimalactone epoxide in vitro, followed by its non-enzymatic conversion to shimalactones in the dark. 相似文献
67.
Dr. Daiki Umeyama Dr. Linn Leppert Bridget A. Connor Dr. Mary Anne Manumpil Prof. Jeffrey B. Neaton Prof. Hemamala I. Karunadasa 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(43):19249-19256
Replacing the Pb−X octahedral building unit of AIPbX3 perovskites (X=halide) with a pair of edge-sharing Pb−X octahedra affords the expanded perovskite analogs: AIIPb2X6. We report seven members of this new family of materials. In 3D hybrid perovskites, orbitals from the organic molecules do not participate in the band edges. In contrast, the more spacious inorganic sublattice of the expanded analogs accommodates larger pyrazinium-based cations with low-lying π* orbitals that form the conduction band, substantially decreasing the band gap of the expanded lattice. The molecular nature of the conduction band allows us to electronically dope the materials by reducing the organic molecules. By synthesizing derivatives with AII=pyridinium and ammonium, we can isolate the contributions of the pyrazinium-based orbitals in the band gap transition of AIIPb2X6. The organic-molecule-based conduction band and the inorganic-ion-based valence band provide an unusual electronic platform with localized states for electrons and more disperse bands for holes upon optical or thermal excitation. 相似文献
68.
Xu Liu Ruoyu Liu Jiaxing Qiu Prof. Dr. Xu Cheng Prof. Dr. Guigen Li 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(33):14066-14071
We report a method for the electrochemical deuteration of α,β-unsaturated carbonyl compounds under catalyst- and external-reductant-free conditions, with deuteration rates as high as 99 % and yields up to 91 % in 2 h. The use of graphite felt for both the cathode and the anode was key to ensuring chemoselectivity and high deuterium incorporation under neutral conditions without the need for an external reductant. This method has a number of advantages over previously reported deuteration reactions that use stoichiometric metallic reductants. Mechanistic experiments showed that O2 evolution at the anode not only eliminates the need for an external reductant but also regulates the pH of the reaction mixture, keeping it approximately neutral. 相似文献
69.
Yunjie Xiang Suoping Peng Shaohui Zheng 《International journal of quantum chemistry》2020,120(1):e26047
Organic solar cell of silol dithiophene based D2-A-D1-A-D2/PC71BM (D: donor part; A: acceptor part; 1 and 2 denote different units) possesses promising power conversion efficiency. Researchers have studied D2-A-D1-A-D2 molecules carefully, including the effects of the different number of terminal thiophenes, the different central moiety (D1), and the length of the alkyl chain. However, there are few investigations, especially theoretical studies, on the influences of different A (acceptor) units on the properties of D2-A-D1-A-D2 molecule. In the present work, we have designed and modeled five new D2-A-D1-A-D2 (D2 = bithiophene and D1 = silol dithiophene) donors by changing A units (A = diketopyrrolopyrrole, naphtho[1,2-c:5,6-c′]bis[1,2,5]thiadiazole, 5-fluoro-2,1,3-benzoselenadiazole, benzobisthiadiazole, and thiazolo[5,4-d]thiazole). We have applied density functional theory (DFT) and time-dependent DFT to predict their ground-state electronic structures and the UV–vis spectra, and the open circuit voltages (Vocs) of organic solar cells of D2-A-D1-A-D2/PC71BM. Based on the calculated results, we find that bithiophene thiazolo[5,4-d]thiazole siloldithiophene (BTTS) (D2 = bithiophene, A = thiazolo[5,4-d]thiazole, D1 = silol dithiophene) possesses the highest lowest unoccupied molecular orbital (−2.60 eV) and the lowest highest occupied molecular orbital (−5.33 eV) energies, and the strongest absorption in the visible region. Besides, the solar cell of BTTS/PC71BM has the highest Voc of 1.02 V. These results indicate that it may be a promising donor. In contrast, bithiophene benzobisthiadiazole siloldithiophene (BBBS) (A = benzobisthiadiazole) has low absorption strength in the visible region, which indicates that it may not be a suitable donor material. 相似文献
70.
Willian Franca 《代数通讯》2018,46(7):2890-2898
Let R be a unital simple ring. Under some technical restrictions, we characterize m-linear mappings G:Rm→R satisfying [G(u,…,u),u]?=?0 for all unit u∈R. 相似文献