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861.
《International journal of quantum chemistry》2018,118(18)
We theoretically design four diaza‐benzo[k]tetraphene‐based diradical isomers ( 1, 2, 3 , and 4 ) with two nitroxide (NO) radical groups as spin sources. The calculations at the B3LYP/6‐311++G(d,p) level suggest that the diaza doping can induce the aromaticity changes and the C C bond rearrangements and, thus, remarkably affect their magnetic coupling magnitudes and even characteristics (ferromagnetic vs. antiferromagnetic). More interestingly, different diaza‐doping positions can lead to distinctly different effects, and further dielectron‐oxidation can also noticeably change the magnetic coupling magnitudes from −919.9 cm−1 ( 1 ) to −158.3 cm−1 ( 1 2+ ) or from −105.1 cm−1 ( 3 ) to −918.9 cm−1 ( 3 2+ ) or induce the magnetic conversions from nonmagnetism ( 2 ) to antiferromagnetism ( 2 2+ , −140.1 cm−1) or from ferromagnetism ( 4 , 108.9 cm−1) to antiferromagnetism ( 4 2+ , −462.5 cm−1). Good matching of two singly occupied molecular orbitals (SOMOs) of the NO groups with the highest occupied molecular orbital (HOMO) of the coupler (for 1 ), or with the lowest unoccupied molecular orbital (LUMO) of the coupler (for 3 2+ and 4 2+ ), available Kekulé structure (for 2 ), aromaticity variations are responsible to strong magnetic couplings. Besides, the HOMO‐LUMO energy gaps of the couplers also considerably affect the magnetic couplings. This work may open a new route for the rational design of the diaza‐benzo[k]tetraphene‐based magnetic molecular modulators or switches. 相似文献
862.
Tingting Fu Janina Oetjen Manuel Chapelle Alexandre Verdu Matthias Szesny Arnaud Chaumot Davide Degli‐Esposti Olivier Geffard Yohann Clment Arnaud Salvador Sophie Ayciriex 《Journal of mass spectrometry : JMS》2020,55(9)
The highly diverse chemical structures of lipids make their analysis directly from biological tissue sections extremely challenging. Here, we report the in situ mapping and identification of lipids in a freshwater crustacean Gammarus fossarum using matrix‐assisted laser desorption/ionization (MALDI) mass spectrometry imaging (MSI) in combination with an additional separation dimension using ion mobility spectrometry (IMS). The high‐resolution trapped ion mobility spectrometry (TIMS) allowed efficient separation of isobaric/isomeric lipids showing distinct spatial distributions. The structures of the lipids were further characterized by MS/MS analysis. It is demonstrated that MALDI MSI with mobility separation is a powerful tool for distinguishing and localizing isobaric/isomeric lipids. 相似文献
863.
Jia‐Rui Wu Bao Li Ying‐Wei Yang 《Angewandte Chemie (International ed. in English)》2020,59(6):2251-2255
Haloalkanes are important chemicals in synthetic chemistry and petrochemical industry, but the separation of their isomers is a big hurdle. Herein, we report a facile energy‐efficient adsorptive separation strategy using a new class of nonporous adaptive crystals based on leaning pillar[6]arene. Desolvated perethylated leaning pillar[6]arene crystals (EtLP6) with interesting nonporous character show a preference for 1‐bromoalkane isomers over 2‐bromoalkane isomers. EtLP6 is capable of separating 1‐bromopropane, 1‐bromobutane, and 1‐bromopentane from the corresponding 1:1 (v/v) mixtures of 1/2‐positional isomers with purities from 89.6 % to 96.3 % in only one adsorption cycle. The selectivity is endowed by the different host–guest binding modes and different stabilities of EtLP6 crystalloids loaded with 1‐ and 2‐positional isomers. Significantly, the guest–adsorbed assemblies are highly stable at room temperature and EtLP6 can be reused many times without any decrease in performance. 相似文献
864.
865.
866.
Boyer JL Polyansky DE Szalda DJ Zong R Thummel RP Fujita E 《Angewandte Chemie (International ed. in English)》2011,50(52):12600-12604
Basic difference: The importance of a pendent base in promoting proton-coupled electron-transfer reactions with low activation barriers has been discussed for H(+) reduction or H(2) oxidation in acetonitrile. Investigation of the interaction between a base positioned in the second coordination sphere of a complex and a water ligand in water oxidation reactions using geometric isomers of [Ru(tpy)(pynap)(OH(2))](2+) (see picture) gave intriguing results. 相似文献
867.
Asaf Ferber Roman Glebov Michael Krivelevich Alon Naor 《Random Structures and Algorithms》2015,46(4):651-676
In this paper we analyze biased Maker‐Breaker games and Avoider‐Enforcer games, both played on the edge set of a random board . In Maker‐Breaker games there are two players, denoted by Maker and Breaker. In each round, Maker claims one previously unclaimed edge of G and Breaker responds by claiming b previously unclaimed edges. We consider the Hamiltonicity game, the perfect matching game and the k‐vertex‐connectivity game, where Maker's goal is to build a graph which possesses the relevant property. Avoider‐Enforcer games are the reverse analogue of Maker‐Breaker games with a slight modification, where the two players claim at least 1 and at least b previously unclaimed edges per move, respectively, and Avoider aims to avoid building a graph which possesses the relevant property. Maker‐Breaker games are known to be “bias‐monotone”, that is, if Maker wins the (1,b) game, he also wins the game. Therefore, it makes sense to define the critical bias of a game, b *, to be the “breaking point” of the game. That is, Maker wins the (1,b) game whenever and loses otherwise. An analogous definition of the critical bias exists for Avoider‐Enforcer games: here, the critical bias of a game b * is such that Avoider wins the (1,b) game for every , and loses otherwise. We prove that, for every is typically such that the critical bias for all the aforementioned Maker‐Breaker games is asymptotically . We also prove that in the case , the critical bias is . These results settle a conjecture of Stojakovi? and Szabó. For Avoider‐Enforcer games, we prove that for , the critical bias for all the aforementioned games is . © 2014 Wiley Periodicals, Inc. Random Struct. Alg., 46,651–676, 2015 相似文献
868.
以3种环糊精衍生物分别涂覆在毛细管内壁制得气相色谱毛细管柱,以正十二烷为溶质,测得理论塔板数均在2800/m以上,柱效较高。研究了它们对一系列苯系物位置异构体的分离性能,探讨了硝基氯苯、硝基苯胺和苯二胺等化合物在不同柱上的拆分机理。底物分子和固定相之间的弱相互作用(如氢键、偶极相互作用和π-π堆积作用)等直接影响毛细管柱对底物的分离性能。对于苯二胺的位置异构体,在全对氯苯异氰酸酯化β-CD涂覆的毛细管柱(ACD)上的分离因子为1.88,在多叠氮β-CD衍生物涂覆的毛细管柱(NMCD)上的分离因子为1.41,但在单叠氮β-CD衍生物涂覆的毛细管柱(NSCD)上无法分开;对于硝基氯苯,在NMCD柱和ACD柱上的分离因子相近(前者为1.13/1.11;后者为1.08/1.15),在NSCD柱上则无分离趋势;对于硝基苯胺,在NMCD柱上无分离趋势。同时,苯环上不同取代基间电子效应则影响了异构体在气相色谱中出峰顺序。 相似文献
869.
Farahnaz Nourmohammadian Issa Yavari Dariush Ajami 《Phosphorus, sulfur, and silicon and the related elements》2013,188(2):443-451
Abstract Ab initio molecular orbital calculations at HF/6-31G*, HF/6-311+G**, and B3LYP/6-311+G** levels of theory for geometry optimization are reported for 1,4-dithiopyrrolo[3,4-c]pyrrole (DtPP, 1) and its twelve structural isomers (2–13). Compounds 1–3 include 2 C─CH and 2 NH─CS structural units. Structural isomers 4–7 include 2 C–CH units, together with 2 NH and 2 C–S groups. Isomers 8–13 possess 2 CH, 2 C, 2 NH, and 2 C─S fragments. According to these calculations, isomers 2, 4, and 8, are more stable than 1. 相似文献
870.
Malek Taher Maghsoodlou Nourollah Hazeri Sayyed Mostafa Habibi Khorasani Hadi Mahmoudi Moghaddam Mahmoud Nassiri Jaber Salehzadeh 《Phosphorus, sulfur, and silicon and the related elements》2013,188(7):1713-1721
Stable crystalline phosphorus ylides containing chlorine and sulfur were obtained in excellent yields from the 1:1:1 addition reaction between triphenylphosphine and dialkyl acetylene-dicarboxylates in the presence of 6-chloro-2-benzoxazolethiol and 2-chloro-phenothiazine. These stable ylides exist in solution as a mixture of two geometrical isomers. This is caused by the conjugation of the ylide moiety with the adjacent carbonyl group, which results in a restricted rotation around the respective carbon-carbon bond. 相似文献