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151.
Long Zhao Ralf I. Kaiser Bo Xu Utuq Ablikim Musahid Ahmed Mikhail M. Evseev Eugene K. Bashkirov Valeriy N. Azyazov Alexander M. Mebel 《Angewandte Chemie (International ed. in English)》2020,59(10):4051-4058
A unified low‐temperature reaction mechanism on the formation of acenes, phenacenes, and helicenes—polycyclic aromatic hydrocarbons (PAHs) that are distinct via the linear, zigzag, and ortho‐condensed arrangements of fused benzene rings—is revealed. This mechanism is mediated through a barrierless, vinylacetylene mediated gas‐phase chemistry utilizing tetracene, [4]phenacene, and [4]helicene as benchmarks contesting established ideas that molecular mass growth processes to PAHs transpire at elevated temperatures. This mechanism opens up an isomer‐selective route to aromatic structures involving submerged reaction barriers, resonantly stabilized free‐radical intermediates, and systematic ring annulation potentially yielding molecular wires along with racemic mixtures of helicenes in deep space. Connecting helicene templates to the Origins of Life ultimately changes our hypothesis on interstellar carbon chemistry. 相似文献
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154.
Golotvin SS Vodopianov E Lefebvre BA Williams AJ Spitzer TD 《Magnetic resonance in chemistry : MRC》2006,44(5):524-538
A unique opportunity exists when an experimental NMR spectrum is obtained for which a specific chemical structure is anticipated. A process of Verification--the confirmation of a postulated structure--is now possible, as opposed to Elucidation-the de novo determination of a structure. A method for automated structure verification is suggested, which compares the chemical shifts, intensities and multiplicities of signals in an experimental 1H NMR spectrum with those from a predicted spectrum for the proposed structure. A match factor (MF) is produced and used to classify the spectrum-structure match into one of three categories, correct, ambiguous, or incorrect. The verification result is also augmented by the spectrum assignment obtained as part of the verification process. This method was tested on a set of synthetic spectra and several sets of experimental spectra, all of which were automatically prepared from raw data. Taking into account even the most problematic structures, with many labile protons present and poor prediction accuracy, 50% of all spectra can still be automatically verified without any false positives or negatives. In a blind test on a typical set of data, it is shown that fewer than 31% of the structures would need manual evaluation. This means that a system is possible whereby 69% of the spectra are prepared and evaluated automatically, and never need to be seen or evaluated by a human. 相似文献
155.
From Spherical to Leaf‐Like Morphologies: Tunable Supramolecular Assembly of Alkynylgold(I) Complexes through Variations of the Alkyl Chain Length 下载免费PDF全文
Eugene Yau‐Hin Hong Dr. Hok‐Lai Wong Prof. Vivian Wing‐Wah Yam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5732-5735
A series of luminescent polynuclear alkynylgold(I) complexes with different lengths of alkyl chains attached at the N‐heterocyclic carbene moieties has been synthesised and demonstrated to display intriguing self‐assembly behaviours through a cooperative growth mechanism. Variation of the alkyl chain length was found to cause drastic morphological differences in the aggregates and to strongly affect the thermodynamic parameters as revealed by the nucleation–elongation model. 相似文献
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157.
Xiaona Wen Yu-Chuan Ou Galina Bogatcheva Giju Thomas Anita Mahadevan-Jansen Bhuminder Singh Eugene C. Lin Rizia Bardhan 《Chemical science》2020,11(36):9863
Rapid and accurate response to targeted therapies is critical to differentiate tumors that are resistant to treatment early in the regimen. In this work, we demonstrate a rapid, noninvasive, and label-free approach to evaluate treatment response to molecular inhibitors in breast cancer (BC) cells with Raman spectroscopy (RS). Metabolic reprogramming in BC was probed with RS and multivariate analysis was applied to classify the cells into responsive or nonresponsive groups as a function of drug dosage, drug type, and cell type. Metabolites identified with RS were then validated with mass spectrometry (MS). We treated triple-negative BC cells with Trametinib, an inhibitor of the extracellular-signal-regulated kinase (ERK) pathway. Changes measured with both RS and MS corresponding to membrane phospholipids, amino acids, lipids and fatty acids indicated that these BC cells were responsive to treatment. Comparatively, minimal metabolic changes were observed post-treatment with Alpelisib, an inhibitor of the mammalian target of rapamycin (mTOR) pathway, indicating treatment resistance. These findings were corroborated with cell viability assay and immunoblotting. We also showed estrogen receptor-positive MCF-7 cells were nonresponsive to Trametinib with minimal metabolic and viability changes. Our findings support that oncometabolites identified with RS will ultimately enable rapid drug screening in patients ensuring patients receive the most effective treatment at the earliest time point.Rapid and accurate response to targeted therapies is critical to differentiate tumors that are resistant to treatment early in the regimen. 相似文献
158.
Panpan Li Quanbin Liang Eugene Yau-Hin Hong Chin-Yiu Chan Yat-Hin Cheng Ming-Yi Leung Mei-Yee Chan Kam-Hung Low Hongbin Wu Vivian Wing-Wah Yam 《Chemical science》2020,11(42):11601
A class of acceptor–donor–acceptor chromophoric small-molecule non-fullerene acceptors, 1–4, with difluoroboron(iii) β-diketonate (BF2bdk) as the electron-accepting moiety has been developed. Through the variation of the central donor unit and the modification on the peripheral substituents of the terminal BF2bdk acceptor unit, their photophysical and electrochemical properties have been systematically studied. Taking advantage of their low-lying lowest unoccupied molecular orbital energy levels (from −3.65 to −3.72 eV) and relatively high electron mobility (7.49 × 10−4 cm2 V−1 s−1), these BF2bdk-based compounds have been employed as non-fullerene acceptors in organic solar cells with maximum power conversion efficiencies of up to 4.31%. Moreover, bistable resistive memory characteristics with charge-trapping mechanisms have been demonstrated in these BF2bdk-based compounds. This work not only demonstrates for the first time the use of a boron(iii) β-diketonate unit in constructing non-fullerene acceptors, but also provides more insights into designing organic materials with multi-functional properties.Boron(iii) β-diketonates have been demonstrated to serve as multi-functional materials in NFA-based OPVs and organic resistive memories. 相似文献
159.
Xiaofeng Wu Jong Min An Jizhen Shang Eugene Huh Sujie Qi Eunhye Lee Haidong Li Gyoungmi Kim Huimin Ma Myung Sook Oh Dokyoung Kim Juyoung Yoon 《Chemical science》2020,11(41):11285
Acetylcholinesterase (AChE) is an extremely critical hydrolase tightly associated with neurological diseases. Currently, developing specific substrates for imaging AChE activity still remains a great challenge due to the interference from butyrylcholinesterase (BChE) and carboxylesterase (CE). Herein, we propose an approach to designing specific substrates for AChE detection by combining dimethylcarbamate choline with a self-immolative scaffold. The representative P10 can effectively eliminate the interference from CE and BChE. The high specificity of P10 has been proved via imaging AChE activity in cells. Moreover, P10 can also be used to successfully map AChE activity in different regions of a normal mouse brain, which may provide important data for AChE evaluation in clinical studies. Such a rational and effective approach can also provide a solid basis for designing probes with different properties to study AChE in biosystems and another way to design specific substrates for other enzymes.In this work, a new approach was developed for designing the representative P10 with high selectivity and sensitivity for imaging AChE activity in the cells and normal mouse brain. 相似文献
160.
Eugene A. Kotomin Yuri A. Mastrikov Rotraut Merkle Joachim Maier 《Current Opinion in Electrochemistry》2020
The efficiency of solid oxide fuel cells (SOFC) depends critically on materials, in particular for the cathode where the oxygen reduction reaction (ORR) occurs. Typically, mixed conducting perovskite ABO3-type materials are used for this purpose. The dominating surface terminations are (001) AO and BO2, with the relative fractions depending on materials composition and ambient conditions.Here, results of recent large-scale first principles (ab initio) calculations for the two alternative polar (La,Sr)O and MnO2 (001) terminations of (La,Sr)MnO3 cathode materials are discussed. The surface oxygen vacancy concentration for the (La,Sr)O termination is more than 5 orders of magnitude smaller compared to MnO2, which leads to drastically decreased estimated ORR rates. Thus, it is predicted for prototypical SOFC cathode materials that the BO2 termination largely determines the ORR kinetics, although with Sr surface segregation (long-term degradation) its fraction of the total surface area decreases, which slows down cathode kinetics. 相似文献