On the Role of Symmetry in Vibrational Strong Coupling: The Case of Charge‐Transfer Complexation

It is well known that symmetry plays a key role in chemical reactivity. Here we explore its role in vibrational strong coupling (VSC) for a charge‐transfer (CT) complexation reaction. By studying the trimethylated‐benzene–I₂ CT complex, we find that VSC induces large changes in the equilibrium constant K_DA of the CT complex, reflecting modifications in the ΔG° value of the reaction. Furthermore, by tuning the microfluidic cavity modes to the different IR vibrations of the trimethylated benzene, ΔG° either increases or decreases depending only on the symmetry of the normal mode that is coupled. This result reveals the critical role of symmetry in VSC and, in turn, provides an explanation for why the magnitude of chemical changes induced by VSC are much greater than the Rabi splitting, that is, the energy perturbation caused by VSC. These findings further confirm that VSC is powerful and versatile tool for the molecular sciences.     

Chemical constituents isolated from stems of Schisandra chinensis and their antifeedant activity against Tribolium castaneum

Abstract

One new sesquiterpene (α-iso-cubebenol acetate, 8), together with 9 known compounds (1-7, 9, 10) were isolated from the stems of Schisandra chinensis (Turcz.) Baill. by repeated silica gel column chromatography. Based on the results of MS, NMR spectra and comparing with literature data, the six dibenzocyclooctadiene lignans were identified as schizandrin A to C (1-3), schizandrin (4), schisantherin A (5) and gomisin J (6), the two sesquiterpenes were identified as α-iso-cubebenol (7) and α-iso-cubebenol acetate (8), while the two triterpenic acids were identified as ganwuweizic acid (9) and kadsuric acid (10). The antifeedant activity of the 10 compounds against Tribolium castaneum adults was tested. Gomisin J (6) exhibited activity at 1500?ppm concentration with 40.3% antifeeding index percentages. As for the dibenzocyclooctene lignans (compounds 1–3, 6), the number of methylenedioxies and the position of hydroxyl groups were the main factors to affect their antifeedant activities.     

Host-Guest Chemistry of Truncated Tetrahedral Imine Cages with Ammonium Ions

Three shape-persistent [4+4] imine cages with truncated tetrahedral geometry with different window sizes were studied as hosts for the encapsulation of tetra-n-alkylammonium salts of various bulkiness. In various solvents the cages behave differently. For instance, in dichloromethane the cage with smallest window size takes up NEt₄⁺ but not NMe₄ ^{+ ,} which is in contrast to the two cages with larger windows hosting both ions. To find out the reason for this, kinetic experiments were carried out to determine the velocity of uptake but also to deduce the activation barriers for these processes. To support the experimental results, calculations for the guest uptakes have been performed by molecular mechanics’ simulations. Finally, the complexation of pharmaceutical interested compounds, such as acetylcholine, muscarine or denatonium have been determined by NMR experiments.     

Stepwise Assembly of Turn-on Fluorescence Sensors in Multicomponent Metal–Organic Frameworks for in Vitro Cyanide Detection

The controlled synthesis of multicomponent metal–organic frameworks (MOFs) allows for the precise placement of multiple cooperative functional groups within a framework, leading to emergent synergistic effects. Herein, we demonstrate that turn-on fluorescence sensors can be assembled by combining a fluorophore and a recognition moiety within a complex cavity of a multicomponent MOF. An anthracene-based fluorescent linker and a hemicyanine-containing CN⁻-responsive linker were sequentially installed into the lattice of PCN-700. The selective binding of CN⁻ to hemicyanine inhibited the energy transfer between the two moieties, resulting in a fluorescence turn-on effect. Taking advantage of the high tunability of the MOF platform, the ratio between anthracene and the hemicyanine moiety could be fine-tuned in order to maximize the sensitivity of the overall framework. The optimized MOF-sensor had a CN⁻-detection limit of 0.05 μm , which is much lower than traditional CN⁻ fluorescent sensors (about 0.2 μm ).     

ZIF-Induced d-Band Modification in a Bimetallic Nanocatalyst: Achieving Over 44 % Efficiency in the Ambient Nitrogen Reduction Reaction

The electrochemical nitrogen reduction reaction (NRR) offers a sustainable solution towards ammonia production but suffers poor reaction performance owing to preferential catalyst–H formation and the consequential hydrogen evolution reaction (HER). Now, the Pt/Au electrocatalyst d-band structure is electronically modified using zeolitic imidazole framework (ZIF) to achieve a Faradaic efficiency (FE) of >44 % with high ammonia yield rate of >161 μg mg_cat⁻¹ h⁻¹ under ambient conditions. The strategy lowers electrocatalyst d-band position to weaken H adsorption and concurrently creates electron-deficient sites to kinetically drive NRR by promoting catalyst–N₂ interaction. The ZIF coating on the electrocatalyst doubles as a hydrophobic layer to suppress HER, further improving FE by >44-fold compared to without ZIF (ca. 1 %). The Pt/Au-N_ZIF interaction is key to enable strong N₂ adsorption over H atom.     

Ionic conductivity study on electron beam irradiated polyacrylonitrile-polyethylene oxide gel

Different mass percent polyacrylonitrile (PAN)-polyethylene oxide (PEO) gels were prepared and irradiated by an electron beam (EB) with energy of 1.0 MeV to the dose ranging from 13 kGy to 260 kGy.The gels were analysed by using Fourier transform infrared spectrum,gel fraction and ionic conductivity (IC) measurement.The results show that the gel is crosslinked by EB irradiation,the crosslinking degree rises with the increasing EB irradiation dose (ID) and the mass percents of both PAN and PEO contribute a lot to the crosslinking;in addition,EB irradiation can promote the IC of PAN-PEO gels.There exists an optimum irradiation dose,at which the IC can increase dramatically.The IC changes of the PAN-PEO gels along with ID are divided into three regions:IC rapidly increasing region,IC decreasing region and IC balanced region.The cause of the change can be ascribed to two aspects,gel capturing electron degree and crosslinking degree.By comparing the IC-ID curves of different mass percents of PAN and PEO in gel,we found that PAN plays a more important role for gel IC promotion than PEO,since addition of PAN in gel causes the IC-ID curve sharper,while addition of PEO in gel causes the curve milder.     

Positive stationary solutions for a diffusive variable-territory prey-predator model

In this paper, we present results on the existence of positive stationary solutions for a diffusive variable-territory prey-predator model in heterogeneous environment, which improve and extend those of Wang and Pang (2009). In addition, the asymptotic behavior of solutions is also analyzed.     

L-fuzzy Q-convergence structures

In this paper, we construct a topological category of pretopological L-fuzzy Q-convergence spaces, which contains the category of topological L-fuzzy Q-convergence spaces as a bireflective full subcategory. Considering the connections with L-fuzzy topology, it is proved that the category of topological L-fuzzy Q-convergence spaces is isomorphic to the category of topological L-fuzzy quasi-coincident neighborhood spaces, and the latter is isomorphic to the category of L-fuzzy topological spaces. Moreover, we find that our pretopological L-fuzzy Q-convergence spaces can be characterized as a kind of L-fuzzy quasi-coincident neighborhood spaces, which is called strong L-fuzzy quasi-coincident neighborhood space.