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81.
The isostatic pressure response of crystalline indole up to 25 GPa was investigated through static geometry optimization using Tkatchenko-Scheffler dispersion-corrected density functional theory method. Different symmetries were identified in the structural evolution with increased pressure, but no motif transition was observed, owing to the stability of the herringbone (HB) motif for small polycyclic aromatic hydrocarbons. Hirshfeld surface analysis determined that there was an increase in the fraction of H···π and π···π contacts within the high pressure structures, while the fraction of H···H contacts was lowered via geometric rearrangements. It was found that isostatic pressure alone, up to 25 GPa, was not sufficient to induce a chemical reaction due to the poor π-orbital overlap existing within the HB motif. However, the applied pressure sets the stage for an activated chemical reaction when the molecules approach each other along the long molecular axis, with a reaction energy and reaction barrier of 1.05 eV and 1.80 eV per molecular unit, respectively. 相似文献
82.
Joanne Lobato Charles Hohensee Bohdan Rhodehamel Jaime Diamond 《Mathematical Thinking and Learning》2013,15(2):85-119
Despite the proliferation of mathematics standards internationally and despite general agreement on the importance of teaching for conceptual understanding, conceptual learning goals for many K-12 mathematics topics have not been well-articulated. This article presents a coherent set of five conceptual learning goals for a complex mathematical domain, generated via a method of systematic empirical analysis of students' reasoning. Specifically, we compared the reasoning of pairs of students who performed differentially on the same task and inferred the pivotal intermediate conceptions that afforded one student deeper engagement with the task than another student. In turn, each pivotal intermediate conception framed an associated conceptual learning goal. While the empirical analysis of student reasoning is typically used to understand how students learn, we argue that such analysis should also play an important role in determining what concepts students should learn. 相似文献
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Dr. Peng Xu Dr. Da Zhao Dr. Florian Berger Aboubakr Hamad Dr. Jens Rickmeier Roland Petzold Mykhailo Kondratiuk Kostiantyn Bohdan Prof. Dr. Tobias Ritter 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(5):1972-1976
Site-selective functionalization of C−H bonds in small complex molecules is a long-standing challenge in organic chemistry. Herein, we report a broadly applicable and site-selective aromatic C−H dibenzothiophenylation reaction. The conceptual advantage of this transformation is further demonstrated through the two-step C−H [18F]fluorination of a series of marketed small-molecule drugs. 相似文献
86.
Domagała S Wieckowska A Kowalski J Rogowska A Szydłowska J Korybut-Daszkiewicz B Bilewicz R Woźniak K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(11):2967-2981
N-Methylated bismacrocyclic Cu and Ni complexes were synthesised and structurally characterised in the solid state. Their properties in solution were analysed by using NMR and ESR spectroscopies and electrochemical methods. Face-to-face biscyclidenes linked through polymethylene chains form rectangular boxlike cations. These moieties can host some small guest molecules (water, pi-electron donating compounds) and are stabilised by a shell of neighbouring counterions. For the bismacrocyclic dinuclear complexes containing two nickel or two copper ions, the intramolecular interactions between the metallic centres are strengthened through methylation of the macrocyclic components, as compared with the nonmethylated species. We report the electron coupling created by two unpaired electrons coming from two copper centres observed by ESR spectroscopy. Methylation weakens the electron-acceptor properties of the complexes, which leads to less effective binding of the pi-electron-donating guests. It also increases the stability of the lower oxidation states. In the case of the copper complexes, both Cu(II)/Cu(I) and Cu(II)/Cu(III) reversible one-electron transfers are seen in the voltammograms. These changes in properties are interpreted as the consequences of steric repulsion between the methyl substituents and the macrocyclic ring. 相似文献
87.
A new type of tubular detector with platinum auxiliary electrode inside the silver amalgam tube (TD+AuxE) was proposed, fabricated, tested and compared with a typical silver amalgam tubular detector developed earlier. Non‐stop‐flow differential pulse voltammetric anodic stripping method (AS‐DPV) and amperometric method in a glucose oxidase biosensor arrangement were tested. Both detectors were applied for AS‐DPV detection in flow systems for the first time. Solutions of zinc and cadmium cations were used as the testing species for voltammetry, and detection of oxygen concentration was used for amperometry. All these experiments require application of highly negative potentials, which is possible to realize with detectors made of silver solid amalgam. The proposed combination of TD+AuxE provides a much greater current response than the arrangement with three individual electrodes. All relevant parameters were optimized for the developed TD+AuxE. The simple and fast measuring protocol for the determination of the zinc content in commercial food supplement tablets has been developed. 相似文献
88.
Metallothioneins (MTs) are widely occurring, small, cysteine‐rich proteins, important for essential metal (Zn, Cu) homeostasis and transport and for heavy metal (Cd, Hg) detoxification. In buffered solutions of mammalian MT, voltammetry and potentiometric striping analysis (PSA) can distinguish different coordination of bound metals or follow their exchange, especially that of zinc and cadmium for copper, silver, and cobalt. The examples of different electrode applications as of hanging mercury drop electrode (HMDE), of silver solid amalgam (AgSAE) electrode, and of silica gel modified carbon paste electrode (SiO2‐CPE) are given. 相似文献
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Bohdan Zelinka 《Czechoslovak Mathematical Journal》2001,51(2):225-229
The signed total domination number of a graph is a certain variant of the domination number. If is a vertex of a graph G, then N() is its oper neighbourhood, i.e. the set of all vertices adjacent to in G. A mapping f: V(G)-1, 1, where V(G) is the vertex set of G, is called a signed total dominating function (STDF) on G, if
for each
V(G). The minimum of values
, taken over all STDF's of G, is called the signed total domination number of G and denoted by st(G). A theorem stating lower bounds for st(G) is stated for the case of regular graphs. The values of this number are found for complete graphs, circuits, complete bipartite graphs and graphs on n-side prisms. At the end it is proved that st(G) is not bounded from below in general. 相似文献