ABSTRACT
The catalytic acceptorless dehydrogenation (ADH) of saturated N-heterocycles has recently gained considerable attention as a promising strategy for hydrogen release from liquid organic hydrogen carriers (LOHCs). Recently, a simple tBuOK base-promoted ADH of N-heterocycles was developed by Yu et al. (Adv. Synth. Catal. 2019, 361, 3958). However, it is still open as to how the tBuOK plays a catalytic role in the ADH process. Herein, our density functional study reveals that the tBuOK catalyzes the ADH of 1,2,3,4-tetrahydroquinoline (THQ) through a quasi-metal-ligand bifunctional catalytic channel or a base-catalyzed pathway with close energy barriers. The hydride transfer in the first dehydrogenation process is determined to be the rate determining step, and the second dehydrogenation can proceed directly from 34DHQ regulated by the tBuOK. In addition, the computational results show that the cooperation of a suitable alkali metal ion with the tBuO- group is so critical that the tBuOLi and the isolated tBuO- are both inferior to tBuOK as a dehydrogenation catalyst.
ABSTRACT
Electron donor-acceptor (EDA) complex photochemistry has become a burgeoning topic in the synthetic radical chemistry mediated by visible light; however, the theoretical insights into the reaction mechanisms are limited. Herein, accurate electronic structure calculations at the CASPT2//CASSCF/PCM level of theory were performed to investigate the paradigm example of EDA complex-enabled photoreaction for visible-light-driven dearomative perfluoroalkylation of ß-naphthol. The excitation energy levels of the EDA complex are controlled by noncovalent interactions because the photoinduced intermolecular charge is enhanced when the noncovalent interaction becomes weaker, leading to the broad spectra ranging from UVA (<380 nm) to visible light (>500 nm). The competitiveness of the radical-radical coupling over the radical chain pathway is also regulated due to the tunable radical concentrations varying the excitation wavelength.
ABSTRACT
The purpose of this work was to study the enhancement effect of chitosan coating on inhibition of deoxynivalenol (DON) accumulation by Litsea cubeba essential oil emulsion during malting. Firstly, the primary emulsion suitable for malting process was screened and the improvement effect of chitosan coating on the properties of primary emulsion was studied. On this basis, chitosan-based Litsea cubeba essential oil emulsion was applied to malting processing. The results showed that the primary emulsion of Litsea cubeba essential oil had good antifungal properties and a minimal effect on the germinability of barley compared with other primary emulsions. The addition of chitosan can improve the physical stability and antifungal ability of the emulsion and reduce the effect of the emulsion on barley germination. When 100 g of chitosan-based Litsea cubeba essential oil emulsion (40 mg/g) was applied to the malting process, the germination rate of barley was 87.7% and the DON concentration of finished malt was reduced to 690 µg/kg, which was 20.9% lower than that of the control. Meanwhile, the other indexes of malt produced by secondary emulsion treatment (after adding chitosan) increased significantly compared with those of malt produced by primary emulsion. This study was of great significance for the application of emulsion to inhibit the accumulation of mycotoxin during malting.
