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941.
Delocalized \begin{document}$\pi_3^6$\end{document} Bond in OX\begin{document}$_2$\end{document} (X=Halogen) Molecules 下载免费PDF全文
Yi-han Tang Pu Yang Meng-yuan Chen Yu-ru Wang Jia-xin Wang Jia-wei Xu 《化学物理学报(中文版)》2022,35(3):542-550
OX\begin{document}$_2$\end{document} (X=halogen) molecules was studied theoretically. Calculation results show that delocalized \begin{document}$\pi_3^6$\end{document} bonds exist in their electronic structures and O atoms adopt the sp\begin{document}$^2$\end{document} type of hybridization, which violates the prediction of the valence shell electron pair repulsion theory of sp\begin{document}$^3$\end{document} type. Delocalization stabilization energy is proposed to measure the contribution of delocalized \begin{document}$\pi_3^6$\end{document} bond to energy decrease and proves to bring extra-stability to the molecule. These phenomena can be summarized as a kind of coordinating effect. 相似文献
942.
Theoretical Investigations on Photodissociation Dynamics of Deuterated Alkyl Halides CD3CH2F 下载免费PDF全文
The product branching ratio between different products in multichannel reactions is as important as the overall rate of reaction, both in terms of practical applications (\emph{e.g}. models of combustion or atmosphere chemistry) in understanding the fundamental mechanisms of such chemical reactions. A global ground state potential energy surface for the dissociation reaction of deuterated alkyl halide CD\begin{document}$ _3 $\end{document} CH\begin{document}$ _2 $\end{document} F was computed at the CCSD(T)/CBS//B3LYP/aug-cc-pVDZ level of theory for all species. The decomposition of CD\begin{document}$ _3 $\end{document} CH\begin{document}$ _2 $\end{document} F is controversial concerning C\begin{document}$ - $\end{document} F bond dissociation reaction and molecular (HF, DF, H\begin{document}$ _2 $\end{document} , D\begin{document}$ _2 $\end{document} , HD) elimination reaction. Rice-Ramsperger-Kassel-Marcus (RRKM) calculations were applied to compute the rate constants for individual reaction steps and the relative product branching ratios for the dissociation products were calculated using the steady-state approach. At the different energies studied, the RRKM method predicts that the main channel for DF or HF elimination from 1, 2-elimination of CD\begin{document}$ _3 $\end{document} CH\begin{document}$ _2 $\end{document} F is through a four-center transition state, whereas D\begin{document}$ _2 $\end{document} or H\begin{document}$ _2 $\end{document} elimination from 1, 1-elimination of CD\begin{document}$ _3 $\end{document} CH\begin{document}$ _2 $\end{document} F occurs through a direct three-center elimination. At 266, 248, and 193 nm photodissociation, the main product CD\begin{document}$ _2 $\end{document} CH\begin{document}$ _2 $\end{document} +DF branching ratios are computed to be 96.57%, 91.47%, and 48.52%, respectively; however, at 157 nm photodissociation, the product branching ratio is computed to be 16.11%. Based on these transition state structures and energies, the following photodissociation mechanisms are suggested: at 266, 248, 193 nm, CD\begin{document}$ _3 $\end{document} CH\begin{document}$ _2 $\end{document} F\begin{document}$ \rightarrow $\end{document} absorption of a photon\begin{document}$ \rightarrow $\end{document} TS5\begin{document}$ \rightarrow $\end{document} the formation of the major product CD\begin{document}$ _2 $\end{document} CH\begin{document}$ _2 $\end{document} +DF; at 157 nm, CD\begin{document}$ _3 $\end{document} CH\begin{document}$ _2 $\end{document} F\begin{document}$ \rightarrow $\end{document} absorption of a photon\begin{document}$ \rightarrow $\end{document} D/F interchange of TS1\begin{document}$ \rightarrow $\end{document} CDH\begin{document}$ _2 $\end{document} CDF\begin{document}$ \rightarrow $\end{document} H/F interchange of TS2\begin{document}$ \rightarrow $\end{document} CHD\begin{document}$ _2 $\end{document} CHDF\begin{document}$ \rightarrow $\end{document} the formation of the major product CHD\begin{document}$ _2 $\end{document} +CHDF. 相似文献
943.
《Arabian Journal of Chemistry》2022,15(1):103464
In the present study, we assessed improvement of anti-inflammatory activity and drug delivery of sulfasalazine (SSZ) by the poly(lactic-co-glycolic acid), (PLGA), in H2O and dichloromethane (DCM) environments via density functional theory (DFT), ADMET, and molecular docking. Our calculated results based on binding energy and thermodynamic parameter represents that the interaction between SSZ and PLGA in Complex A via double hydrogen bonds is stronger in comparison with Complex B. The analysis of Ultraviolet–visible (UV–VIS) spectra proved the interaction of SSZ with PLGA by time-dependent density functional theory (TDDFT). Infrared (IR) spectra demonstrated that the structure of PLGA was shifted in the presence of the SSZ. The interaction of SSZ with PLGA leads to an increase in dipole moment and higher solubility with more negative Gibbs free solvation energy (ΔGsolv) values and lowering of the energy gap (Eg). The obtained results by Molecular docking demonstrates that the interaction of SSZ via its carboxylate group with PLGA (complex A) had a strong interaction towards the binding pocket of the target and as a potential inhibitor of the COX-2, TNF-α, and IL-1 receptors at the binding site as compared with the complex B. 相似文献
944.
To date, luminescent materials have been preferably used for non-contact optical thermometers. In this manner, novel red-emitting Ba2Y0.8Eu0.2NbO6:Mn4+ (BYEN:Mn4+) phosphors were designed for multi-type non-contact luminescent thermometers based on the dual-emission states and temperature-dependent lifetime (TDL) models. In the temperature range of 303–483 K, the sensing sensitivities based on the dual-emission states of (5D0→7F2, 2Eg→4A2g) and (5D0→7F1, 2Eg→4A2g) were estimated. Especially, the maximum absolute sensing sensitivity (Sa) was found to be about 0.1558 K-1 for the BYEN:0.007Mn4+ phosphor based on the 5D0→7F1 and 2Eg→4A2g positions. This phosphor also exhibited good relative sensing sensitivity (Sr) (0.0186 K-1) based on the 5D0→7F2 and 2Eg→4A2g states. Besides, the relative sensing sensitivities (SR) at 5D0→7F1 and 2Eg→4A2g transitions were estimated to be 0.0034 and 0.0194 K-1, respectively with the help of the TDL technique. In the light of these results, novel red-emitting Ba2Y0.8Eu0.2NbO6:Mn4+ phosphors are expected to be a potentially attractive candidate for applications in multi-type luminescent thermometers. Finally, a novel unique polydimethylsiloxane film exhibiting tricolor-luminescent emissions was introduced and further suggested for high-security anti-counterfeiting. 相似文献
945.
Supercapacitors (SCs) with high energy density and power density are a research hotspot. Herein, we report a flexible porous carbon membrane supercapacitor prepared by electrospinning polyacrylonitrile (PAN) with γ-cyclodextrin-MOF (γ-CD-MOF) and then carbonizing at 900 °C. BET results showed that the supercapacitor retained the skeleton of γ-CD, γ-CD-MOF and the pores formed by the spun-fibers, which were 0.73, 1.09 and 23–186 nm, respectively, showing a high specific surface area of 134.7 m2/g. The hierarchically porous structures ensure rapid charge transfer and ion diffusion, resulting in the PAN/γ-CD-MOF carbon electrode with a high capacity of 283.3 F/g. Moreover, the supercapacitor had a high energy density up to 17.5 Wh/kg and power density up to 6 kW/kg. Significantly, it showed excellent cycle stability with a capacitance retention of 97.5% after 6000 cycles. This work provides a supramolecular strategy to construct a flexible porous carbon membrane, which has potential for supercapacitor applications. 相似文献
946.
Rituparno Chowdhury Venkata Sai Sreyas Adury Amal Vijay Reman K. Singh Arnab Mukherjee 《化学:亚洲杂志》2021,16(12):1634-1642
Computational drug design is increasingly becoming important with new and unforeseen diseases like COVID-19. In this study, we present a new computational de novo drug design and repurposing method and applied it to find plausible drug candidates for the receptor binding domain (RBD) of SARS-CoV-2 (COVID-19). Our study comprises three steps: atom-by-atom generation of new molecules around a receptor, structural similarity mapping to existing approved and investigational drugs, and validation of their binding strengths to the viral spike proteins based on rigorous all-atom, explicit-water well-tempered metadynamics free energy calculations. By choosing the receptor binding domain of the viral spike protein, we showed that some of our new molecules and some of the repurposable drugs have stronger binding to RBD than hACE2. To validate our approach, we also calculated the free energy of hACE2 and RBD, and found it to be in an excellent agreement with experiments. These pool of drugs will allow strategic repurposing against COVID-19 for a particular prevailing conditions. 相似文献
947.
Svitlana V. Shishkina Irina S. Konovalova Svitlana S. Kovalenko Lyudmila L. Nikolaeva Natalya D. Bunyatyan Sergiy M. Kovalenko 《Acta Crystallographica. Section C, Structural Chemistry》2021,77(1):20-28
The dipharmacophore compound 3‐cyclopropyl‐5‐(3‐methyl‐[1,2,4]triazolo[4,3‐a]pyridin‐7‐yl)‐1,2,4‐oxadiazole, C12H11N5O, was studied on the assumption of its potential biological activity. Two polymorphic forms differ in both their molecular and crystal structures. The monoclinic polymorphic form was crystallized from more volatile solvents and contains a conformer with a higher relative energy. The basic molecule forms an abundance of interactions with relatively close energies. The orthorhombic polymorph was crystallized very slowly from isoamyl alcohol and contains a conformer with a much lower energy. The basic molecule forms two strong interactions and a large number of weak interactions. Stacking interactions of the `head‐to‐head' type in the monoclinic structure and of the `head‐to‐tail' type in the orthorhombic structure proved to be the strongest and form stacked columns in the two polymorphs. The main structural motif of the monoclinic structure is a double column where two stacked columns interact through weak C—H…N hydrogen bonds and dispersive interactions. In the orthorhombic structure, a single stacked column is the main structural motif. Periodic calculations confirmed that the orthorhombic structure obtained by slow evaporation has a lower lattice energy (0.97 kcal mol?1) compared to the monoclinic structure. 相似文献
948.
Christian Balischewski Hyung-Seok Choi Karsten Behrens Alkit Beqiraj Thomas Körzdörfer André Geßner Dr. Armin Wedel Prof. Dr. Andreas Taubert 《ChemistryOpen》2021,10(2):272-295
Metal sulfides are among the most promising materials for a wide variety of technologically relevant applications ranging from energy to environment and beyond. Incidentally, ionic liquids (ILs) have been among the top research subjects for the same applications and also for inorganic materials synthesis. As a result, the exploitation of the peculiar properties of ILs for metal sulfide synthesis could provide attractive new avenues for the generation of new, highly specific metal sulfides for numerous applications. This article therefore describes current developments in metal sulfide nanoparticle synthesis as exemplified by a number of highlight examples. Moreover, the article demonstrates how ILs have been used in metal sulfide synthesis and discusses the benefits of using ILs over more traditional approaches. Finally, the article demonstrates some technological challenges and how ILs could be used to further advance the production and specific property engineering of metal sulfide nanomaterials, again based on a number of selected examples. 相似文献
949.
Energy storage using dielectric capacitors is a growing area of research and development. However, designing a highly performing dielectric capacitor is still a challenge. Despite the excellent results achieved in lead-based dielectrics, lead-free substitutes are essential because of the environmental concerns associated with lead-based products. The lead-free 1?x (0.94NaNbO3? 0.06SrZrO3)+ x Bi2O3 ceramics abbreviated NNSZ + xB for x = 0.0, 0.05, 0.1, 0.15, and 0.20 was fabricated via solid-state reaction. A recoverable energy density of 2.93 J cm?3 was obtained for NNSZ+0.1B, associated with high thermal stability (25–130 °C), excellent cycling (N = 105), and high efficiency (η) of 83.5%. Moreover, the introduction of Bi2O3 significantly improved the electrical insulation (?r at 1 kHz = 1608 and tan δ = 0.0038) and breakdown strength (380 kVcm?1) of NNSZ+0.1B by minimizing the formation of sodium, bismuth, and oxygen vacancies. The results obtained in this study provide a benchmark for further investigations on NaNbO3-based ceramics. More importantly, this study suggests that NNSZ + xB ceramics can be used in pulsed power technology. 相似文献
950.
Enhanced Static Modulated Fourier Transform Spectrometer for Fast Approximation in Field Application
We discuss the data sampling frequency, the spectral resolution, and the limit for non-aliasing in the static modulated Fourier transform spectrometer based on a modified Sagnac interferometer. The measurement was performed in a very short 4 ms, which is applicable for real time field operation. The improved spectrometer characteristics were used to investigate the spectral properties of an InGaAs light emitting diode. In addition, The measured spectral peak was shifted from 6420 cm−1 to 6365 cm−1, as the temperature increased from 25 °C to 40 °C, when the operating current is fixed to be 0.55 A. As the applied current increased from 0.30 A to 0.55 A at room temperature, the spectral width was broadened from 316 cm−1 to 384 cm−1. Compared to the conventional Fourier transform spectrometer, the measured spectral width by the static modulated Fourier transform spectrometer showed a deviation less than 10%, and the spectral peak shift according to the temperature rise showed a difference within 2%. 相似文献