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Dr. Zaifa Shi Dr. Yihuang Jiang Dr. Jingxiong Yu Prof. Shanjun Chen Prof. Jun Chen Prof. Zichao Tang Prof. Lansun Zheng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(8):e202103546
At present, the reactivity of cyclic alkanes is estimated by comparison with acyclic hydrocarbons. Due to the difference in the structure of cycloalkanes and acycloalkanes, the thermodynamic data obtained by analogy are not applicable. In this study, a molecular beam sampling vacuum ultraviolet photoionization time-of-flight mass spectrometer (MB-VUV-PI-TOFMS) was applied to study the low-temperature oxidation of cyclopentane (CPT) at a total pressure range from 1–3 atm and low-temperature range between 500 and 800 K. Low-temperature reaction products including cyclic olefins, cyclic ethers, and highly oxygenated intermediates (e. g., ketohydroperoxide KHP, keto-dihydroperoxide KDHP, olefinic hydroperoxides OHP and ketone structure products) were observed. Further investigation of the oxidation of CPT – electronic structure calculations – were carried out at the UCCSD(T)-F12a/aug-cc-pVDZ//B3LYP/6-31+ G(d,p) level to explore the reactivity of O2 molecules adding sequentially to cyclopentyl radicals. Experimental and theoretical observations showed that the dominant product channel in the reaction of CPT radicals with O2 is HO2 elimination yielding cyclopentene. The pathways of second and third O2 addition – the dissociation of hydroperoxide – were further confirmed. The results of this study will develop the low-temperature oxidation mechanism of CPT, which can be used for future research on accurately simulating the combustion process of CPT. 相似文献
3.
Dominik Vítek Prof. Aleš Růžička Lise Vermeersch Dr. Libor Dostál Dr. Jan Turek Prof. Roman Jambor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202202639
Reactivity studies of the GeII→B complex L(Cl)Ge⋅BH3 ( 1 ; L=2-Et2NCH2-4,6-tBu2-C6H2) were performed to determine the effect on the GeII→B donation. N-coordinated compounds L(OtBu)Ge⋅BH3 ( 2 ) and [LGe⋅BH3]2 ( 3 ) were prepared. The possible tuning of the GeII→B interaction was proved experimentally, yielding compounds 1-PPh2-8-(LGe)-C10H6 ( 4 ) and L(Cl)Ge⋅GaCl3 ( 5 ) without a GeII→B interaction. In 5 , an unprecedented GeII→Ga coordination was revealed. The experimental results were complemented by a theoretical study focusing on the bonding in 1 − 5 . The different strength of the GeII→E (E=B, Ga) donation was evaluated by using energy decomposition analysis. The basicity of different L(X)Ge groups through proton affinity is also assessed. 相似文献
4.
《Mendeleev Communications》2022,32(4):534-536
Correlation times and diffusion coefficients of water molecules were measured for the first time by 1H spin relaxation and pulsed field gradient NMR in Li+, Na+ and Cs+ ionic forms of Nafion 117 membrane. Hydration numbers of Li+, Na+ and Cs+ cations were calculated. It was shown that at high humidity macroscopic transfer is controlled by the local translational motion of water molecules. 相似文献
5.
Dr. Jordan Donat Mr. Patrick Dubourdeaux Dr. Martin Clémancey Dr. Julia Rendon Clara Gervasoni Mr. Morgan Barbier Jessica Barilone Dr. Jacques Pécaut Prof. Dr. Serge Gambarelli Prof. Dr. Pascale Maldivi Prof. Dr. Jean-Marc Latour 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202201875
Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from FeII and FeIII precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an FeIV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the FeII precursor was expected by a two-electron oxidative addition, its formation from an FeIII precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the FeIII precursor, an FeIII tosyliodinane adduct was formed and decomposed into an FeV tosylimido species which generated the catalytically active FeIV tosylimide through a comproportionation process with the FeIII precursor. 相似文献
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7.
《Operations Research Letters》2022,50(2):137-144
In mine planning problems, cutoff grade optimization defines a threshold at every time period such that material above this value is processed, and the rest is considered waste. In orebodies with multiple minerals, which occur in practice, the natural extension is to consider a cutoff surface. We show that in two dimensions the optimal solution is a line, and in n dimensions it is a hyperplane. 相似文献
8.
This paper infers from a generalized Picone identity the uniqueness of the stable positive solution for a class of semilinear equations of superlinear indefinite type, as well as the uniqueness and global attractivity of the coexistence state in two generalized diffusive prototypes of the symbiotic and competing species models of Lotka–Volterra. The optimality of these uniqueness theorems reveals the tremendous strength of the Picone identity. 相似文献
9.
Tomoyuki Nakatsuka 《Mathematische Nachrichten》2021,294(1):98-117
We study the existence of a time‐periodic solution with pointwise decay properties to the Navier–Stokes equation in the whole space. We show that if the time‐periodic external force is sufficiently small in an appropriate sense, then there exists a time‐periodic solution of the Navier–Stokes equation such that and uniformly in as . Our solution decays faster than the time‐periodic Stokes fundamental solution and the faster decay of its spatial derivatives of higher order is also described. 相似文献
10.
《Annales de l'Institut Henri Poincaré (C) Analyse Non Linéaire》2021,38(5):1337-1371
In this paper we consider minimizers of the functional where is a bounded open set and where are the first k eigenvalues on Ω of an operator in divergence form with Dirichlet boundary condition and with Hölder continuous coefficients. We prove that the optimal sets have finite perimeter and that their free boundary is composed of a regular part, which is locally the graph of a -regular function, and a singular part, which is empty if , discrete if and of Hausdorff dimension at most if , for some . 相似文献