Low-Pressure Sensitive Piezochromic Fluorescence Switching of Tetraphenylethylene-Anthraquinone.

Invited for the cover of this issue are Prof. Wenjing Tian and co-workers at Jilin University. The image depicts the highly sensitive piezochromic fluorescence switching of tetraphenylethylene-anthraquinone under low-pressure regimes (∼60 kPa). Read the full text of the article at 10.1002/chem.202301070.

Low-Pressure Sensitive Piezochromic Fluorescence Switching of Tetraphenylethylene-Anthraquinone.

Sensing of low-pressure signals is of great importance for cutting-edge technologies. Organic piezochromic molecules offer a promising library of pressure sensitive materials which can be tailor-designed toward specific requirements. However, very few examples of low-pressure sensitive piezochromic fluorescent molecules have been obtained till date, and the underlying mechanisms are still in its infancy. Herein, we report highly sensitive piezochromic fluorescent switching under low-pressure regimes (∼60 kPa) of tetraphenylethylene-anthraquinone (TPE-AQ) based on the controlled molecular design and polymorphic phase strategy. The influence of both intramolecular conformation effect and variations of intermolecular stacking modes on the piezochromic property of TPE-AQ is investigated. The underlying mechanism of the low-pressure sensitive piezochromic fluorescence switching is demonstrated to be closely related to the loosely packed molecular orientation, as confirmed by X-ray diffraction measurements combined with simulations. This work provides a way to design highly efficient pressure sensors based on organic molecular systems.

Enhancement of Circularly Polarized Luminescence from Pulsating Nanotubules.

Enhancing the dissymmetry factor (glum ) is a crucial issue in developing circularly polarized luminescence (CPL) materials. Herein, based on supramolecular self-assembly of diethyl l-glutamate-cyanodiarylethene (L-GC) in mixed solution of EtOH-H2 O with different water fraction, enhanced circularly polarized emission from pulsating nanotubules is realized. In the mixture of ethanol and water (30/70, v/v), L-GC self-assembles into roll-up-type dense nanotubes and shows l-CPL. Remarkably, by increasing the water fraction to 80% and 90%, the diameter of the roll-up nanotubes increases and the dissymmetry factor of the nanotubes is significantly enhanced from 6.9 × 10-3  (dense nanotubes) to 3.7 × 10-2 (loose nanotubes) because of the enhanced intermolecular interactions and more ordered supramolecular stacking when increasing the water fraction. An efficient way is provided here to realize the increase of the dissymmetry factor by only changing the composition of solvents.

Efficient production of Aschersonia placenta protoplasts for transformation using optimization algorithms.

The insect pathogenic fungus Aschersonia placenta is a highly effective pathogen of whiteflies and scale insects. However, few genetic tools are currently available for studying this organism. Here we report on the conditions for the production of transformable A. placenta protoplasts using an optimized protocol based on the response surface method (RSM). Critical parameters for protoplast production were modelled by using a Box-Behnken design (BBD) involving 3 levels of 3 variables that was subsequently tested to verify its ability to predict protoplast production (R(2) = 0.9465). The optimized conditions resulted in the highest yield of protoplasts ((4.41 ± 0.02) × 10(7) cells/mL of culture, mean ± SE) when fungal cells were treated with 26.1 mg/mL of lywallzyme for 4 h of digestion, and subsequently allowed to recover for 64.6 h in 0.7 mol/L NaCl-Tris buffer. The latter was used as an osmotic stabilizer. The yield of protoplasts was approximately 10-fold higher than that of the nonoptimized conditions. Generated protoplasts were transformed with vector PbarGPE containing the bar gene as the selection marker. Transformation efficiency was 300 colonies/(µg DNA·10(7) protoplasts), and integration of the vector DNA was confirmed by PCR. The results show that rational design strategies (RSM and BBD methods) are useful to increase the production of fungal protoplasts for a variety of downstream applications.

Circularly Polarized Luminescence Switching Driven by Precisely Tuned Supramolecular Interactions: From Hydrogen Bonding to π-π Interaction.

It is highly challenging to achieve circularly polarized luminescence (CPL) switching by precisely tuning supramolecular interactions and unveiling the mechanism of supramolecular chirality inversion. Herein, we demonstrated CPL switching based on diethyl l-glutamate-9-cyanophenanthrene (LGCP) and diethyl l-glutamate-pyrene (LGP) via the precise regulation of supramolecular interactions. LGCP assembly driven by hydrogen bonding showed right CPL, while LGP assembly driven by π-π interaction led to left CPL. Remarkably, significant CPL switching was observed from the assemblies of LGCP/octafluoronaphthalene (OFN), attributed to the alteration of the dominating interaction from weak hydrogen bonding to rather strong π-π interaction, while the assemblies of LGP/OFN exhibited minimum CPL variation because the dominating π-π interaction within the assembly of LGP/OFN illustrated quite limited variations upon arene-perfluoroarene interaction. This work provides a feasible strategy toward the efficient modulation of the chiroptical properties of multiple component supramolecular systems, meanwhile offering possibilities for the mechanism exploration of the chirality inversion of supramolecular assemblies.

Extraction, identification and antimicrobial activity of a new furanone, grifolaone A, from Grifola frondosa.

A furanone (1), (S)-methyl 2-(2-hydroxy-3,4-dimethyl-5-oxo-2,5-dihydrofuran-2-yl)acetate, was isolated from the edible mushroom Grifola frondosa. Mass spectrometry and NMR analyses were used to elucidate the structure of this compound, and its absolute configuration was determined using circular dichroism spectroscopy. Compound 1 exhibited specific antifungal activity against the plant pathogens, Fusarium oxysporum, Gibberella zeae and Piricularia oryzae and the opportunistic human pathogen, Pseudallescheria boydii, resulting in minimum inhibitory concentration values of 2.5, 2.5, 1.25 and 0.15 µg/mL, respectively. In contrast, the furanone showed only weak activity towards Aspergillus spp., Candida albicans and several other fungal strains tested as well as no appreciable antibacterial activity.

A new azaphilone from the entomopathogenic fungus Hypocrella sp.

This report describes the isolation of a new azaphilone, designated hypocrellone A (2), together with five known compounds (1, 3-6) from a submerged culture of the entomopathogenic fungus Hypocrella sp. (isolate WYTY-21). The absolute stereostructures of the two compounds (1 and 2) were elucidated based on 1D and 2D NMR spectroscopic and mass spectrometric data combined with the data from various chemical transformations. Hypocrellone A (2) and three (3-6) of the five known compounds were cytotoxic to hepatoma cells (cell line BEL-7404); IC50 values ranged from 6.2 to 17.4 µM. At 200 µM, none of the six compounds was toxic to normal human liver cells (cell line HL-7702) or to normal human kidney epithelial cells (cell line HEK-293T).