Faced with the contradictory results of two recent experimental studies [Jara‐Toro et al., Angew. Chem. Int. Ed. 2017 , 56, 2166 and Chao et al., Angew. Chem. Int. Ed. 2019 , 58, 5013] of the possible catalytic effect of water vapor on CH3OH + OH reaction, we report calculations that corroborate the conclusion made by Chao et al. and extend the rate constant evaluation down to 200 K. The rate constants of the CH3OH + OH reaction catalyzed by a water molecule are computed as functions of temperature and relative humidity using high‐level electronic structure and kinetics calculations. The Wuhan–Minnesota Scaling (WMS) method is used to provide accurate energetics to benchmark a density functional for direct dynamics. Both high‐frequency and low‐frequency anharmonicities are included. Variational and tunneling effects are treated by canonical variational transition state theory with multidimensional small‐curvature tunneling. And, most significantly, we include multistructural effects in the rate constant calculations. Our calculations show that the catalytic effect of water vapor is not observable at 200–400 K. 相似文献
A divergent synthetic approach to six Ganoderma meroterpenoids, namely ganocins A–C, ganocochlearins C and D, and cochlearol T, has been developed for the first time. This synthetic route features a two‐phase strategy which includes early‐stage rapid construction of a common planar tricyclic intermediate followed by highly selective late‐stage transformations into various Ganoderma meroterpenoids. Key to the strategy are a bioinspired intramolecular hetero‐Diels–Alder reaction and Stahl‐type oxidative aromatization, allowing efficient formation of the common tricyclic phenol intermediate. A nucleophilic dearomatization of the phenol unit, combined with a regioselective 1,4‐reduction of the resulting dienone, enabled rapid access to ganocins B and C. Additionally, site‐selective Mukaiyama hydration, followed by an intramolecular oxa‐Michael addition/triflation cascade, served as a key strategic element in the chemical synthesis of ganocin A. 相似文献
34,354,966 active cases and 460,787 deaths because of COVID-19 pandemic were recorded on November 06, 2021, in India. To end this ongoing global COVID-19 pandemic, there is an urgent need to implement multiple population-wide policies like social distancing, testing more people and contact tracing. To predict the course of the pandemic and come up with a strategy to control it effectively, a compartmental model has been established. The following six stages of infection are taken into consideration: susceptible (S), asymptomatic infected (A), clinically ill or symptomatic infected (I), quarantine (Q), isolation (J) and recovered (R), collectively termed as SAIQJR. The qualitative behavior of the model and the stability of biologically realistic equilibrium points are investigated in terms of the basic reproduction number. We performed sensitivity analysis with respect to the basic reproduction number and obtained that the disease transmission rate has an impact in mitigating the spread of diseases. Moreover, considering the non-pharmaceutical and pharmaceutical intervention strategies as control functions, an optimal control problem is implemented to mitigate the disease fatality. To reduce the infected individuals and to minimize the cost of the controls, an objective functional has been constructed and solved with the aid of Pontryagin’s maximum principle. The implementation of optimal control strategy at the start of a pandemic tends to decrease the intensity of epidemic peaks, spreading the maximal impact of an epidemic over an extended time period. Extensive numerical simulations show that the implementation of intervention strategy has an impact in controlling the transmission dynamics of COVID-19 epidemic. Further, our numerical solutions exhibit that the combination of three controls are more influential when compared with the combination of two controls as well as single control. Therefore, the implementation of all the three control strategies may help to mitigate novel coronavirus disease transmission at this present epidemic scenario.
Experiment and simulation were used to study the flow fields of a liquid-solid-solid three-phase system in a draft-tube stirred reactor with a six-flat-bladed t... 相似文献
Meccanica - Self-excited oscillation induced by the internal frictions of spline joints is a major cause of rotor system instability. In this study, the dynamic equations of spline-connected... 相似文献
In this work, Monte Carlo simulations are used to study the critical adsorption behaviors of flexible polymer chains under the action of an external driving force F parallel to an attractive flat surface. The critical adsorption temperature T_c decreases linearly with increasing F,indicating that the driving force suppresses the adsorption of polymer. The conformation of polymer is also affected by the driving force.However, the effect of F is dependent on the competition between the driving force and temperature. Under strong force or at low temperature,the polymer is stretched along the direction of the force, while under weak force or at high temperature, the polymer is not stretched. When the force is comparable to the temperature, the polymer may be stretched perpendicular to the driving force, and below T_c, we observe conformational transitions from parallel to perpendicular and again to parallel by decreasing the temperature. We found that the perpendicular stretched conformation leads the polymer chain to synchronously move along the direction of the driving force. Moreover, the conformational transitions are attributed to the competition and cooperation between the driving force and the temperature. 相似文献
Listeria monocytogenes (L. monocytogenes) is an important Gram-positive food-borne pathogen that severely threatens public health. A checkerboard microdilution method was performed to evaluate the synergistic effect of lithocholic acid (LCA) with Gentamicin (Genta) against L. monocytogenes. BacLight LIVE/DEAD staining, scanning electron microscopy and biofilm inhibition assays were further used to explore the bactericidal effect and antibiofilm effect of this combination on L. monocytogenes. Additionally, the synergistic effects of LCA derivatives with Genta were also evaluated against L. monocytogenes, S.aureus and S. suis. The results indicated that a synergistic bactericidal effect was observed for the combined therapy of LCA at the concentration without affecting bacteria viability, with Genta. Additionally, LCA in combination with Genta had a synergistic effect against Gram-positive bacteria (L. monocytogenes, S. aureus and S. suis) but not against Gram-negative bacteria (E. coli, A. baumannii and Salmonella). BacLight LIVE/DEAD staining and scanning electron microscopy analysis revealed that the combination of LCA with Genta caused L. monocytogenes membrane injury, leading to bacteria death. We found that 8 μg/mL LCA treatment effectively improved the ability of Genta to eradicate L. monocytogenes biofilms. In addition, we found that chenodeoxycholic acid, as a cholic acid derivative, also improved the bactericidal effect of Genta against Gram-positive bacteria. Our results indicate that LCA represents a broad-spectrum adjuvant with Genta for infection caused by L. monocytogenes and other Gram-positive pathogens. 相似文献
In this paper, let m ≥ 1 be an integer, M be an m-dimensional compact Riemannian manifold.Firstly the linearized Poincaré map of the Lagrangian system at critical point x ■ is explicitly given, then we prove that Morse index and Maslov-type index of x are well defined whether the manifold M is orientable or not via the parallel transport method which makes no appeal to unitary trivialization and establish the relation of Morse index and Maslov-type index, finally derive a criterion for the instability of critical point and orientation of M and obtain the formula for two Maslov-type indices. 相似文献